The Phoenix Wet Chemistry Laboratory (WCL)

During the summer of 2008 the Phoenix Mars Lander acquired and analyzed samples of soil and ice to investigate the presence of water in all its phases and the historical record preserved in the chemistry and mineralogy of the soil. It also addressed biohabitability by; identifying potential chemical energy sources available to support life; analyzing for organics; and identifying the potential of the geochemical environment to preserve paleontological evidence.

To analyze the chemistry of the soil, Phoenix carried with it a Wet Chemistry Laboratory (WCL) consisting of four identical cells (Figure 1), each comprised of a lower "beaker" containing a set of chemical sensors designed to analyze the chemical properties of the soil, and an upper "actuator" for adding soil, water, reagents, and stirring. Each beaker contained an array of sensors consisting of solid state and PVC-membrane based ion selective electrodes (ISE) that analyzed for inorganic anions and cations, including Ca2+, Mg2+, K+, Na+, NH4+, Cl-, Br-, I-, NO3-, ClO4-, and SO4=. The array also included electrodes for pH, conductivity, oxidation-reduction potential (Eh), anodic stripping voltammetry (ASV) for heavy metals, chronopotentiometry (CP) for independent determination of chloride, bromide and iodide, and cyclic voltammetry (CV) for identifying and analyzing possible reversible and irreversible redox couples.

The upper assembly consisted of a sealed, Teflon-coated, titanium leaching solution reservoir (water plus ionic species for initial sensor calibration), a sample drawer designed to receive the soil through a screened funnel from the robotic arm, remove excess soil, and deposit 1 cm3 of soil into the beaker containing 25 mL of water; a stirrer motor with impeller; and a reagent dispenser that held five crucibles consisting of a second calibration reagent, an acid, and three packed with barium chloride for determination of sulfate. A complete description of the WCL has been published, both as part of Phoenix mission [1] and the previous cancelled 2001 MSP mission [2].

Figure 1. Left: An individual Wet Chemistry Laboratory (WCL) showing the main components. Right Top: Placement of the electrods inside the beaker wall. Right Bottom: Diagram of an ion-selective electrode.

In June of 2008, sol 30 on Mars, the Wet Chemistry Laboratory (WCL) performed the first wet chemical analysis of a soil on another planet to determine its soluble components (Figure 2). The WCL's first analysis of a 1 cc soil sample produced major new scientific findings that have changed the way we view the aqueous geochemistry of Mars.  The data from this array of ISE sensors provided new scientific insights into the history of the planet, its potential for supporting microbial life, and its atmospheric chemistry. The analyses on three soil samples, two from the surface and one from 5 cm depth, revealed a slightly alkaline soil with a pH of ~7.7 (±0.3), an average conductivity of ~1.4 (±0.5) mS/cm for the 1:25 soil/solution mixture, and the presence in solution of Ca2+, Mg2+, K+, Na+, Cl-, SO4=, and most unexpectedly, perchlorate (ClO4-) [3,4]. Three regolith (soil) samples were analyzed, Rosy Red (RR), Sorceress-1 (S1), and Sorceress-2 (S2). The drawers for RR and S2 were observed to be full (1 cc of soil). The density was estimated to be 1 g/cc based on Viking 1/2 data. For S1 the volume was estimated as ~ 0.75 cc since it appeared that the drawer was 75% full. The WCL solution concentrations for RR, S1, and S2 were measured as 2.7 mM, 2.2. mM, and 2.5 mM, respectively. These translate into 0.67 wt%, 0.68 wt%, and 0.62 wt% ClO4- in the soil, respectively [3,3A]. Analyses of the WCL data have also shown that the soil contained at least 1.3 (±0.5) wt% of soluble SO4= [5], that the redox potential (Eh) of the soil/water mixture in the WCL was 253 (±0.5) mV [6], and that the parent salts of the ClO4- are most likely a mixture of 60% Ca(ClO4)2 and 40% Mg(ClO4)2 [7]. The best estimate we have for the concentrations of the species present in the solution, and in the martian soil at the Phoenix site, are given in Table 1 of reference [5].

The presence of perchlorate on Mars has also been confirmed by its detection in the Mars meteorites EETA79001 [8] and Tissint [9], and by the Sample Analysis at Mars (SAM) instrument on the Curiosity rover [10]. It has been shown that the perchlorate on Mars is likely produced by the action of UV irradiation on chloride-bearing mineral surfaces [11]. During this process several ClOx intermediates such as hypochlorite (ClO-), chlorite (ClO2-), chlorate (ClO3-), and chlorine dioxide (ClO2) gas, as well as radicals such as ClO-, O2-, ‧OCl, ‧Cl, and ‧OH are also likely generated [12-14]. These intermediate products can alter or destroy organic compounds, with only highly refractory and/or those well protected from UV surviving.

Figure 2. First of three successful deliveries to the first WCL unit on sol-30


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[1] S. P. Kounaves, et al., "The MECA Wet Chemistry Laboratory on the 2007 Phoenix Mars Scout Lander", J. Geophys. Res., 114, 2009, E00A19, doi:10.1029/2008JE003084. FullText

[2] S. P. Kounaves, et al.,"Mars Surveyor Program '01 Mars Environmental Compatibility Assessment Wet Chemistry Lab: A Sensor Array for Chemical Analysis of the Martian Soil", J. Geophys. Res., 2003, 108(E7), 5077-89. Full Text

[3] S. P. Kounaves, et al., "Wet Chemistry Experiments on the 2007 Phoenix Mars Scout Lander: Data Analysis and Results" J. Geophys. Res., 2010, 115, E00E10, doi:10.1029/2009JE003424 Full Text

[3A] B. Sutter, R. C. Quinn, P. D. Archer, D. P. Glavin, T. D. Glotch, S. P. Kounaves, M. M. Osterloo, E. B. Rampe, and D. W. Ming, "Measurements of Oxychlorine species on Mars", Int. J. Astrobiol., 2016, 16(3), 203-217, Full Text.

[4] M. H. Hecht, S. P. Kounaves, et al., "Detection of Perchlorate and the Soluble Chemistry of Martian Soil at the Phoenix Lander Site", Science, 2009, 325, 64-67. Full Text

[5] S. P. Kounaves, et al., "Soluble Sulfate in the Martian Soil at the Phoenix Landing Site", Geophys. Res. Lett., 2010, 37, L09201, doi:10.1029/2010GL042613. Full Text

[6] R. C. Quinn, J. D. Chittenden, S. P. Kounaves, and M. H. Hecht, "The Oxidation‐Reduction Potential of Aqueous Soil Solutions at the Mars Phoenix Landing Site" Geophys. Res. Lett., 2011, 38, L14202, doi:10.1029/2011GL047671. Full Text

[7] S. P. Kounaves, et al., "Identification of the Perchlorate Parent Salts at the Phoenix Mars Landing Site and Possible Implications", Icarus, 2014, 232, 226-231, doi:10.1016/j.icarus.2014.01.016 Full Text

[8] S. P. Kounaves, et al., "Evidence of Martian Perchlorate, Chlorate, and Nitrate in Mars Meteorite EETA79001: Implications for Oxidants and Organics”, Icarus, 2014, 229, 206-213, doi:10.1016/j.icarus.2013.11.012 Full Text

[9] E. A. Jaramillo, S. H. Royle, M. W. Claire, S. P. Kounaves,& M. A. Sephton, "Indigenous Organic-Oxidized Fluid Interactions in the Tissint Mars Meteorite" Geophys. Res. Lett., 2019, 46(6), 3090-3098, doi:10.1029/2018gl081335. Full Text

[10] D. P. Glavin, et al., "Evidence for perchlorates and the origin of chlorinated hydrocarbons detected by SAM at the Rocknest aeolian deposit in Gale Crater", J. Geophys. Res., 2013, 118, 1955-1973. Full Text

[11] B. L. Carrier and S. P. Kounaves,"The Origins of Perchlorate in the Martian Soil",Geophys. Res. Lett., 2015, 42, 3746-3754, doi:10.1002/2015GL064290 Full Text

[12] D. Liu and S. P. Kounaves, "The Production of Perchlorate from Chlorite and Chlorate on Earth and Mars", ACS Earth Space Chem. 2019, 3, 1678-1684, doi:10.1021/acsearthspacechem.9b00134. Full Text

[13] D. Liu and S. P. Kounaves, "Degradation of Amino Acids on Mars by UV Irradiation in the Presence of Chloride and Oxychlorine Salts", Astrobiology. 2021, 21, 793-801. doi:10.1089/ast.2020.2328. Full Text

[14] J. Newmark, and S. P. Kounaves, "Permeation of photochemically-generated gaseous chlorine dioxide on Mars as a significant factor in destroying subsurface organic compounds", Nature Sci. Rep., 2004,14:7682, doi:10.1038/s41598-024-57968-1 Full Text

 

Last Updated 12/19/2024