[Show abstract][Hide abstract] ABSTRACT: Abstract Life-detection instruments on future Mars missions may use surfactant solutions to extract organic matter from samples of martian rocks. The thermal and radiation environments of space and Mars are capable of degrading these solutions, thereby reducing their ability to dissolve organic species. Successful extraction and detection of biosignatures on Mars requires an understanding of how degradation in extraterrestrial environments can affect surfactant performance. We exposed solutions of the surfactants polysorbate 80 (PS80), Zonyl FS-300, and poly[dimethylsiloxane-co-[3-(2-(2-hydroxyethoxy)ethoxy)propyl]methylsiloxane] (PDMSHEPMS) to elevated radiation and heat levels, combined with prolonged storage. Degradation was investigated by measuring changes in pH and electrical conductivity and by using the degraded solutions to extract a suite of organic compounds spiked onto grains of the martian soil simulant JSC Mars-1. Results indicate that the proton fluences expected during a mission to Mars do not cause significant degradation of surfactant compounds. Solutions of PS80 or PDMSHEPMS stored at -20°C are able to extract the spiked standards with acceptable recovery efficiencies. Extraction efficiencies for spiked standards decrease progressively with increasing temperature, and prolonged storage at 60°C renders the surfactant solutions ineffective. Neither the presence of ascorbic acid nor the choice of solvent unequivocally alters the efficiency of extraction of the spiked standards. Since degradation of polysorbates has the potential to produce organic compounds that could be mistaken for indigenous martian organic matter, the polysiloxane PDMSHEPMS may be a superior choice of surfactant for the exploration of Mars. Key Words: Mars-Life detection-Surfactants-Life Marker Chip. Astrobiology 14, xxx-xxx.
[Show abstract][Hide abstract] ABSTRACT: The first step in many life detection protocols on Mars involves attempts to extract or isolate organic matter from its mineral matrix. A number of extraction options are available and include heat and solvent assisted methods. Recent operations on Mars indicate that heating samples can cause the loss or obfuscation of organic signals from target materials, raising the importance of solvent-based systems for future missions. Several solvent types are available (e.g. organic solvents, surfactant based solvents and subcritical water extraction) but a comparison of their efficiencies in Mars relevant materials is missing. We have spiked the well characterised Mars analogue material JSC Mars-1 with a number of representative organic standards. Extraction of the spiked JSC Mars-1 with the three solvent methods provides insights into the relative efficiency of these methods and indicates how they may be used on future Mars missions.
Planetary and Space Science 09/2014; 99. DOI:10.1016/j.pss.2014.05.001 · 1.88 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The search for life on Mars requires instruments that detect organic
matter and discriminate between potential sources. One such instrument
is the life marker chip that recognizes small molecules which are
characteristic of particular organic provenances. The use of an
antibody-based detection system requires the delivery of small organic
compounds in a suitable solvent. Dedicated extraction protocols have
been developed partly through the use of a life marker chip breadboard
system. Techniques which provide the strong diagnostic potential of the
life marker chip necessitate appropriate sample types. Clay mineral-rich
rocks are attractive targets owing to their (i) association with liquid
water, (ii) propensity for organic matter and clay mineral co-deposition
following transport from a wide hinterland, and (iii) relatively large
surface area and therefore potential for trapping/adsorption of organic
materials. The most appropriate target organic compounds are the
hydrocarbon-dominated lipids that can be highly diagnostic and have
relatively high preservation potentials. The sample sites on Mars and
sample preparation steps that are needed for successful detection
require careful consideration. In this paper we explore the scientific
results that may be obtained through the operation of a life marker chip
instrument on Mars.
Planetary and Space Science 09/2013; 86:66-74. DOI:10.1016/j.pss.2013.04.016 · 1.88 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Abstract The Life Marker Chip (LMC) instrument is an immunoassay-based sensor that will attempt to detect signatures of life in the subsurface of Mars. The molecular reagents at the core of the LMC have no heritage of interplanetary mission use; therefore, the design of such an instrument must take into account a number of risk factors, including the radiation environment that will be encountered during a mission to Mars. To study the effects of space radiation on immunoassay reagents, primarily antibodies, a space study was performed on the European Space Agency's 2007 BIOPAN-6 low-Earth orbit (LEO) space exposure platform to complement a set of ground-based radiation studies. Two antibodies were used in the study, which were lyophilized and packaged in the intended LMC format and loaded into a custom-made sample holder unit that was mounted on the BIOPAN-6 platform. The BIOPAN mission went into LEO for 12 days, after which all samples were recovered and the antibody binding performance was measured via enzyme-linked immunosorbent assays (ELISA). The factors expected to affect antibody performance were the physical conditions of a space mission and the exposure to space conditions, primarily the radiation environment in LEO. Both antibodies survived inactivation by these factors, as concluded from the comparison between the flight samples and a number of shipping and storage controls. This work, in combination with the ground-based radiation tests on representative LMC antibodies, has helped to reduce the risk of using antibodies in a planetary exploration mission context. Key Words: Low-Earth orbit-Radiation-Life-detection instruments-Spaceflight-Mars. Astrobiology 13, xxx-xxx.
[Show abstract][Hide abstract] ABSTRACT: Some life detection instruments under development for operation on Mars use solvents to extract organic compounds from samples of Martian regolith and rock and to transfer the extracts to dedicated detectors. However, it is possible that organic compounds extracted from Martian samples and dissolved in the solvent could adsorb to instrument surfaces, potentially resulting in a failure to detect organic matter that could have been avoided by using more appropriate instrument materials. If successful detection and characterisation is to take place it is therefore essential to understand the interactions between dissolved organic targets and the surfaces of space instrument components. One such life detection instrument is the Life Marker Chip (LMC) being developed for the ExoMars mission, which relies on a novel surfactant-based solvent system and antibody-based detectors. We have tested the ability of a range of materials, including titanium, stainless steel, aluminium, the fluoropolymer Viton™, polytetrafluoroethylene (PTFE), nylon, polypropylene, polyethersulfone and cellulose acetate to adsorb a range of organic standards from the surfactant solution intended to be used by the LMC. Results indicate that aromatic hydrocarbons, specifically anthracene, are more prone to adsorption than straight chain, branched and cyclic aliphatic species. Titanium, aluminium and stainless steel show little adsorption ability and are suitable for larger-area applications. PTFE and Viton™ are suitable for use in small-area applications such as seals and filters. Nylon, polypropylene, polyethersulfone and cellulose acetate show stronger adsorption characteristics and should be avoided in the forms employed here. The ability of some materials to selectively adsorb organic compounds from solvent extracts can lower the sensitivity of life detection instruments. In future, it would be prudent to test all space instrument materials for their ability to adsorb target organic compounds from the solvent systems with which they will be used. This work has application beyond LMC and is relevant to future life detection instruments and their associated cleaning procedures that use solvents. The findings will also be pertinent to planned sample return missions involving caching and can inform the selection of materials used in sample return containers and during the subsequent processing of any returned samples.
Planetary and Space Science 12/2012; 73(1):262–270. DOI:10.1016/j.pss.2012.08.023 · 1.88 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The Life Marker Chip (LMC) is one of the instruments being developed for
possible flight on the 2018 ExoMars mission. The instrument uses
solvents to extract organic compounds from samples of martian regolith
and to transfer the extracts to dedicated detectors based around the use
of antibodies. The scientific aims of the instrument are to detect
organics in the form of biomarkers that might be associated with extinct
life, extant life or abiotic sources of organics. The instrument relies
on a novel surfactant-based solvent system and bespoke, commercial and
research-developed antibodies against a number of distinct biomarkers or
molecular types. The LMC comprises of a number of subsystems designed to
accept up to four discrete samples of martian regolith or crushed rock,
implement the solvent extraction, perform microfluidic-based multiplexed
antibody-assays for biomarkers and other targets, optically detect the
fluorescent output of the assays, control the internal instrument
pressure and temperature, in addition to the associated instrument
control electronics and software. The principle of operation, the design
and the instrument development status as of December 2011 are reported
here. The instrument principle can be extended to other configurations
and missions as needed.
Planetary and Space Science 11/2012; 72(1):129–137. DOI:10.1016/j.pss.2012.04.007 · 1.88 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Abstract The Life Marker Chip (LMC) instrument is part of the proposed payload on the ESA ExoMars rover that is scheduled for launch in 2018. The LMC will use antibody-based assays to detect molecular signatures of life in samples obtained from the shallow subsurface of Mars. For the LMC antibodies, the ability to resist inactivation due to space particle radiation (both in transit and on the surface of Mars) will therefore be a prerequisite. The proton and neutron components of the mission radiation environment are those that are expected to have the dominant effect on the operation of the LMC. Modeling of the radiation environment for a mission to Mars led to the calculation of nominal mission fluences for proton and neutron radiation. Various combinations and multiples of these values were used to demonstrate the effects of radiation on antibody activity, primarily at the radiation levels envisaged for the ExoMars mission as well as at much higher levels. Five antibodies were freeze-dried in a variety of protective molecular matrices and were exposed to various radiation conditions generated at a cyclotron facility. After exposure, the antibodies' ability to bind to their respective antigens was assessed and found to be unaffected by ExoMars mission level radiation doses. These experiments indicated that the expected radiation environment of a Mars mission does not pose a significant risk to antibodies packaged in the form anticipated for the LMC instrument. Key Words: Life-detection instruments-Planetary habitability and biosignatures-Radiation-Mars-Life in extreme environments. Astrobiology 12, 718-729.
[Show abstract][Hide abstract] ABSTRACT: The Life Marker Chip is being designed to detect the chemical evidence
of life in the martian soil. It will use an aqueous surfactant solution
to extract polar and nonpolar biomarkers from the martian soil and to
transport them into an antibody-based detector for characterisation.
Currently, a solution of 1.5 g l-1 polysorbate 80 in 20:80
(vol:vol) methanol:water is being considered and appears to be suitable.
Here, we have investigated the ability of a range of other surfactant
solutions to extract a suite of eight standards spiked on the surfaces
of the martian soil simulant JSC Mars-1 and tested the compatibility of
the best two surfactants with a representative antibody assay for the
detection of pyrene. The results show that using 20:80 (vol:vol)
methanol:water as the solvent leads to increased recoveries of standards
than using water alone. The poloxamer surfactants
Pluronic® F-68 and Pluronic® F-108 are not
effective at extracting the standards from JSC Mars-1 at any of the
concentrations tested here. The fluorosurfactant Zonyl®
FS-300 is able to extract the standards, but not as efficiently as
polysorbate 80 solutions. Most successful of the alternative surfactants
was the polysiloxane
(PDMSHEPMS) which is able to extract the standards from JSC Mars-1 with
an efficiency approximately equal to that of polysorbate 80 solutions of
the same concentration. Enhanced recovery of the standards using
polysorbate 80 and PDMSHEPMS solutions can be achieved by increasing the
concentration of surfactant, from 1.5 g l-1 to 10 g
l-1, leading to an increase in the recovery of standards of
about 50%. Polysorbate 80 at concentrations of 1.5 g l-1 and
10 g l-1 and Zonyl® FS-300 and PDMSHEPMS (both
at a concentration of 10 g l-1) are also compatible with the
representative pyrene antibody assay.
Planetary and Space Science 07/2012; 67(1):109-118. DOI:10.1016/j.pss.2012.03.006 · 1.88 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Beagle 2 lander is a flight qualified scientific payload and it offers a
unique suite of instruments which can offer answers to the life on Mars
question. Using multiple Beagle 2 landers on Mars offers a low-cost and
outstanding scientific option.
[Show abstract][Hide abstract] ABSTRACT: The Life Marker Chip (LMC) is being developed for the 2018 ExoMars mission for the detection of multiple organic molecules, e.g. biomarkers of life, in rock and regolith samples using low temperature solvent extraction and multiplexed immunoassays.
[Show abstract][Hide abstract] ABSTRACT: In the present study, five different classes of small hydrophobic molecular targets, atypical for antibody generation, were structurally modified in order to introduce suitable reactive functionalities and/or spacers which allow covalent coupling to a carrier protein resulting in a stable carrier-hapten complex. These targets were chosen to serve as markers of extant and/or extinct life in the context of the development of the Life Marker Chip (LMC), an antibody-based instrument, which is being developed by a UK-led international consortium for flight to Mars on board the joint ESA/NASA Mars exploration ExoMars mission. The hapten-protein conjugates were designed to be used as immunogens for antibody generation and immunoassay reagents in subsequent stages of the LMC development. The extent of protein modification due to covalent attachment of hapten was determined by two independent methods, i.e. trinitrobenzenesulfonic acid (TNBSA) titrations of remaining protein reactive groups and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) of the resultant hapten-protein conjugates. In a further quality validation step, the conjugates were presented to an animal's immune system and polyclonal antibody titres with moderate specificity were obtained. These results suggest that conjugates synthesized as described herein can successfully be used in the generation of antibodies targeting small hydrophobic molecules.
[Show abstract][Hide abstract] ABSTRACT: The proposed ExoMars mission, due to launch in 2018, aims to look for evidence of extant and extinct life in martian rocks and regolith. Previous attempts to detect organic molecules of biological or abiotic origin on Mars have been unsuccessful, which may be attributable to destruction of these molecules by perchlorate salts during pyrolysis sample extraction techniques. Organic molecules can also be extracted and measured with solvent-based systems. The ExoMars payload includes the Life Marker Chip (LMC) instrument, capable of detecting biomarker molecules of extant and extinct Earth-like life in liquid extracts of martian samples with an antibody microarray assay. The aim of the work reported here was to investigate whether the presence of perchlorate salts, at levels similar to those at the NASA Phoenix landing site, would compromise the LMC extraction and detection method. To test this, we implemented an LMC-representative sample extraction process with an LMC-representative antibody assay and used these to extract and analyze a model sample that consisted of a Mars analog sample matrix (JSC Mars-1) spiked with a representative organic molecular target (pyrene, an example of abiotic meteoritic infall targets) in the presence of perchlorate salts. We found no significant change in immunoassay function when using pyrene standards with added perchlorate salts. When model samples spiked with perchlorate salts were subjected to an LMC-representative liquid extraction, immunoassays functioned in a liquid extract and detected extracted pyrene. For the same model sample matrix without perchlorate salts, we observed anomalous assay signals that coincided with yellow coloration of the extracts. This unexpected observation is being studied further. This initial study indicates that the presence of perchlorate salts, at levels similar to those detected at the NASA Phoenix landing site, is unlikely to prevent the LMC from extracting and detecting organic molecules from martian samples.
[Show abstract][Hide abstract] ABSTRACT: We present the scientific case for inclusion of penetrators into the Europan surface, and the candidate instruments which could significantly enhance the scientific return of the joint ESA/NASA Europa-Jupiter System Mission (EJSM). Moreover, a surface element
would provide an exciting and inspirational mission highlight which would encourage public and political support for the mission.
Whilst many of the EJSM science goals can be achieved from the proposed orbital platform, only surface elements can provide key
exploration capabilities including direct chemical sampling and associated astrobiological material detection, and sensitive habitability
determination. A targeted landing site of upwelled material could provide access to potential biological material originating from deep
beneath the ice.
Penetrators can also enable more capable geophysical investigations of Europa (and Ganymede) interior body structures, mineralogy,
mechanical, magnetic, electrical and thermal properties. They would provide ground truth, not just for the orbital observations of
Europa, but could also improve confidence of interpretation of observations of the other Jovian moons. Additionally, penetrators on
both Europa and Ganymede, would allow valuable comparison of these worlds, and gather significant information relevant to future landed missions. The advocated low mass penetrators also offer a comparatively low cost method of achieving these important science
A payload of two penetrators is proposed to provide redundancy, and improve scientific return, including enhanced networked seismometer
performance and diversity of sampled regions.
We also describe the associated candidate instruments, penetrator system architecture, and technical challenges for such penetrators,
and include their current status and future development plans.
Advances in Space Research 08/2011; 48(2011-4):725-742. DOI:10.1016/j.asr.2010.06.026 · 1.36 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Emplacement of four or more kinetic penetrators geographically distributed over the lunar surface can enable a broad range
of scientific exploration objectives of high priority and provide significant synergy with planned orbital missions. Whilst
past landed missions achieved a great deal, they have not included a far-side lander, or investigation of the lunar interior
apart from a very small area on the near side. Though the LCROSS mission detected water from a permanently shadowed polar
crater, there remains in-situ confirmation, knowledge of concentration levels, and detailed identification of potential organic
chemistry of astrobiology interest. The planned investigations will also address issues relating to the origin and evolution
of the Earth–Moon system and other Solar System planetary bodies. Manned missions would be enhanced with use of water as a
potential in-situ resource; knowledge of potential risks from damaging surface Moonquakes, and exploitation of lunar regolith
for radiation shielding. LunarNet is an evolution of the 2007 LunarEX proposal to ESA (European Space Agency) which draws
on recent significant advances in mission definition and feasibility. In particular, the successful Pendine full-scale impact
trials have proved impact survivability for many of the key technology items, and a penetrator system study has greatly improved
the definition of descent systems, detailed penetrator designs, and required resources. LunarNet is hereby proposed as an
exciting stand-alone mission, though is also well suited in whole or in-part to contribute to the jigsaw of upcoming lunar
missions, including that of a significant element to the ILN (International Lunar Network).
[Show abstract][Hide abstract] ABSTRACT: The life marker chip (LMC) is being designed to test for the chemical signature of life in the soil and rocks of Mars. It will use an antibody array as part of its detection and characterisation system and aims to detect both polar and non-polar molecules at the sub-ppm to tens of ppb level. It is necessary to use a solvent to transfer organic compounds from the Martian samples to the LMC itself, but organic solvents such as dichloromethane or hexane, commonly used to dissolve non-polar molecules, are incompatible with the LMC antibodies. Hence, an aqueous-based solvent capable of dissolving the biomarkers that might exist in the soil or rocks of Mars is required. Solvent extractions of a Martian soil analogue, JSC Mars-1, spiked with a range of standards show that a 20:80 (vol:vol) mixture of methanol and water is incapable of extracting compounds insoluble in water. However, addition of 1.5 mg ml−1 of the surfactant polysorbate 80 produces extraction efficiencies of the aliphatic standards, hexadecane and phytane, equal to 25–30% of those produced by the common organic solvent mixture 93:7 (vol:vol) dichloromethane:methanol. Extraction of squalene and stigmasterol using the polysorbate solution is less efficient but still successful, at 5–10% of the efficiency of 93:7 dichloromethane:methanol. Such aliphatic compounds with occasional functional groups represent the compound classes to which most fossil organic biomarkers belong. The polysorbate solution did not extract the aromatic compounds pyrene and anthracene with great efficiency. A solvent of 20:80 methanol:water with 1.5 mg ml−1 polysorbate 80 is therefore capable of selectively extracting aliphatic biomarkers from Martian samples and transferring them to the antibody sites on the life marker chip.
Planetary and Space Science 09/2010; 58(11):1470-1474. DOI:10.1016/j.pss.2010.07.004 · 1.88 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The Gas Analysis Package and associated instruments from Beagle 2 is the ideal payload to measure the abundances and isotopic compositions of ice and volatiles found in the polar regions of the Moon. The hardware has already been flight qualified.
[Show abstract][Hide abstract] ABSTRACT: The absolute chronology of Mars is poorly known and, as a consequence, a key science aim is to perform accurate radiometric dating of martian geological materials. The scientific benefits of in situ radiometric dating are significant and arguably of most importance is the calibration of the martian cratering rate, similar to what has been achieved for the Moon, to reduce the large uncertainties on absolute boundary ages of martian epochs. The Beagle 2 Mars lander was capable of performing radiometric date measurements of rocks using the analyses from two instruments in its payload: (i) the X-ray Spectrometer (XRS) and (ii) the Gas Analysis Package (GAP). We have investigated the feasibility of in situ radiometric dating using the K-Ar technique employing flight-like versions of Beagle 2 instrumentation. The K-Ar ages of six terrestrial basalts were measured and compared to the ‘control’ Ar-Ar radiometric ages in the range 171–1141 Ma. The K content of each basalt was measured by the flight spare XRS and the 40Ar content using a laboratory analogue of the GAP. The K-Ar ages of five basalts broadly agreed with their corresponding Ar-Ar ages. For one final basalt, the 40Ar content was below the detection limit and so an age could not be derived. The precision of the K-Ar ages was ∼30% on average. The conclusions from this study are that careful attention must be paid to improving the analytical performance of the instruments, in particular the accuracy and detection limits. The accuracy of the K and Ar measurements are the biggest source of uncertainty in the derived K-Ar age. Having investigated the technique using flight-type planetary instrumentation, we conclude that come of the principle challenges of conducting accurate in situ radiometric dating on Mars using instruments of these types include determining the sample mass, ensuring all the argon is liberated from the sample given the maximum achievable temperature of the mass spectrometer ovens, and argon loss and non-radiogenic argon in the analysed samples.
Planetary and Space Science 09/2009; 57(11-57):1237-1245. DOI:10.1016/j.pss.2009.02.012 · 1.88 Impact Factor