Performance evaluation of a miniature laser ablation time-of-flight mass spectrometer designed for in situ investigations in planetary space research

Key performance features of a miniature laser ablation time-of-flight mass spectrometer designed for in situ investigations of the chemical composition of planetary surfaces are presented. This mass spectrometer is well suited for elemental and isotopic analysis of raw solid materials with high sensitivity and high spatial resolution. In this study, ultraviolet laser radiation with irradiances suitable for ablation (< 1 GW/cm2) is used to achieve stable ion formation and low sample consumption. In comparison to our previous laser ablation studies at infrared wavelengths, several improvements to the experimental setup have been made, which allow accurate control over the experimental conditions and good reproducibility of measurements. Current performance evaluations indicate significant improvements to several instrumental figures of merit. Calibration of the mass scale is performed within a mass accuracy (Δm/m) in the range of 100 ppm, and a typical mass resolution (m/Δm) ~600 is achieved at the lead mass peaks. At lower laser irradiances, the mass resolution is better, about (m/Δm) ~900 for lead, and limited by the laser pulse duration of 3 ns. The effective dynamic range of the instrument was enhanced from about 6 decades determined in previous study up to more than 8 decades at present. Current studies show high sensitivity in detection of both metallic and non-metallic elements. Their abundance down to tens of ppb can be measured together with their isotopic patterns. Due to strict control of the experimental parameters, e.g. laser characteristics, ion-optical parameters and sample position, by computer control, measurements can be performed with high reproducibility. Copyright © 2012 John Wiley & Sons, Ltd.

Self-supporting CVD diamond charge state conversion surfaces for high resolution imaging of low-energy neutral atoms in space plasmas

Two polycrystalline diamond surfaces, manufactured by chemical vapour deposition (CVD) technique, are investigated regarding their applicability as charge state conversion surfaces (CS) for use in a low energy neutral atom imaging instrument in space research. The capability of the surfaces for converting neutral atoms into negative ions via surface ionisation processes was measured for hydrogen and oxygen with particle energies in the range from 100 eV to 1 keV and for angles of incidence between 6 deg and 15 deg. We observed surface charging during the surface ionisation processes for one of the CVD samples due to low electrical conductivity of the material. Measurements on the other CVD diamond sample resulted in ionisation efficiencies of ~2 % for H and up to 12 % for O. Analysis of the angular scattering revealed very narrow and almost circular scattering distributions. Comparison of the results with the data of the CS of the IBEX-Lo sensor shows that CVD diamond has great potential as CS material for future space missions.

High-Resolution Chemical Depth Profiling of Solid Material Using a Miniature Laser Ablation/Ionization Mass Spectrometer

High-resolution chemical depth profiling measurements of copper films are presented. The 10 μm thick copper test samples were electrodeposited on a Si-supported Cu seed under galvanostatic conditions in the presence of particular plating additives (SPS, Imep, PEI, and PAG) used in the semiconductor industry for the on-chip metallization of interconnects. To probe the trend of these plating additives toward inclusion into the deposit upon growth, quantitative elemental mass spectrometric measurements at trace level concentration were conducted by using a sensitive miniature laser ablation ionization mass spectrometer (LIMS), originally designed and developed for in situ space exploration. An ultrashort pulsed laser system (τ ∼ 190 fs, λ = 775 nm) was used for ablation and ionization of sample material. We show that with our LIMS system, quantitative chemical mass spectrometric analysis with an ablation rate at the subnanometer level per single laser shot can be conducted. The measurement capabilities of our instrument, including the high vertical depth resolution coupled with high detection sensitivity of ∼10 ppb, high dynamic range ≥10(8), measurement accuracy and precision, is of considerable interest in various fields of application, where investigations with high lateral and vertical resolution of the chemical composition of solid materials are required, these include, e.g., wafers from semiconductor industry or studies on space weathered samples in space research.

A Review of General Physical and Chemical Processes Related to Plasma Sources and Losses for Solar System Magnetospheres

The aim of this paper is to provide a review of general processes related to plasma sources, their transport, energization, and losses in the planetary magnetospheres. We provide background information as well as the most up-to-date knowledge of the comparative studies of planetary magnetospheres, with a focus on the plasma supply to each region of the magnetospheres. This review also includes the basic equations and modeling methods commonly used to simulate the plasma sources of the planetary magnetospheres. In this paper, we will describe basic and common processes related to plasma supply to each region of the planetary magnetospheres in our solar system. First, we will describe source processes in Sect. 1. Then the transport and energization processes to supply those source plasmas to various regions of the magnetosphere are described in Sect. 2. Loss processes are also important to understand the plasma population in the magnetosphere and Sect. 3 is dedicated to the explanation of the loss processes. In Sect. 4, we also briefly summarize the basic equations and modeling methods with a focus on plasma supply processes for planetary magnetospheres.

Chemical Composition of Micrometer-Sized Filaments in an Aragonite Host by a Miniature Laser Ablation/Ionization Mass Spectrometer

Detection of extraterrestrial life is an ongoing goal in space exploration, and there is a need for advanced instruments and methods for the detection of signatures of life based on chemical and isotopic composition. Here, we present the first investigation of chemical composition of putative microfossils in natural samples using a miniature laser ablation/ionization time-of-flight mass spectrometer (LMS). The studies were conducted with high lateral (similar to 15 mu m) and vertical (similar to 20-200 nm) resolution. The primary aim of the study was to investigate the instrument performance on micrometer-sized samples both in terms of isotope abundance and element composition. The following objectives had to be achieved: (1) Consider the detection and calculation of single stable isotope ratios in natural rock samples with techniques compatible with their employment of space instrumentation for biomarker detection in future planetary missions. (2) Achieve a highly accurate chemical compositional map of rock samples with embedded structures at the micrometer scale in which the rock matrix is easily distinguished from the micrometer structures. Our results indicate that chemical mapping of strongly heterogeneous rock samples can be obtained with a high accuracy, whereas the requirements for isotope ratios need to be improved to reach sufficiently large signal-to-noise ratio (SNR). Key Words: Biogenicity-Biomarkers-Biosignatures-Filaments-Fossilization. Astrobiology 15, 669-682.

Chemical and isotopic compositions of basalts and glasses from lavas of the Sierra Leone fault site

According to detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial rift zone of the MAR between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts, but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in basalts and their glasses. It was shown that some samples have significant nonsystematic differences in the 87Sr/86Sr ratio between basalts and their chilled glasses and less significant difference in e-Nd; higher Sr ratios can be observed both in glasses and basalts of the same lava fragments. No significant correlation is observed between isotope characteristics of samples and their geochemistry; it was also shown that seawater did not affect Sr and Nd isotope compositions of the chilled glasses from the studied pillow lavas. It is suggested that such differences in isotope ratios are related to small-scale heterogeneity of melts owing to incomplete homogenization during their rapid ascent to the surface. Heterogeneity of basaltic melts is explained by their partial contamination by older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the surface of the ocean floor. The wider scatter of the Sr isotopic ratios relative to Nd ones is related to presence of xenocrysts of calcic plagioclase; correspondingly, absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. Causes of this phenomenon remain unclear.

Concentrations and accumulation rates of chemical elements and sediment components in sediments of central equatorial Pacific, DSDP data

Accumulation rates of Mg, Al, Si, Mn, Fe, Ni, Cu, Zn, opal, and calcium carbonate have been calculated from their concentrations in samples from equatorial Deep Sea Drilling Project sites. Maps of element accumulation rates and of Q-mode factors derived from raw data indicate that the flux of trace metals to equatorial Pacific sediments has varied markedly through time and space in response to changes in the relative and absolute influence of several depositional influences: biogenic, detrital, authigenic, and hydrothermal sedimentation. Biologically derived material dominates the sediment of the equatorial Pacific. The distributions of Cu and Zn are most influenced by surface-water biological activity, but Ni, Al, Fe, and Mn are also incorporated into biological material. All of these elements have equatorial accumulation maxima similar to those of opal and calcium carbonate at times during the past 50 m.y. Detritus distributed by trade winds and equatorial surface circulation contributes Al, non-biogenic Si, Fe, and Mg to the region. Detrital sediment is most important in areas with a small supply of biogenic debris and low bulk-accumulation rates. Al accumulation generally increases toward the north and east, indicating its continental source and distribution by the northeast trade winds. Maxima in biological productivity during middle Eocene and latest Miocene to early Pliocene time and concomitant well-developed surface circulation contributed toward temporal maxima in the accumulation rates of Cu, Zn, Ni, and Al in sediments of those ages. Authigenic material is also important only where bulk-sediment accumulation rates are low. Ni, Cu, Zn, and sometimes Mn are associated with this sediment. Fe is almost entirely of hydrothermal origin. Mn is primarily hydrothermal, but some is probably scavenged from sea water by amorphous iron hydroxide floes along with other elements concentrated in hydrothermal sediments, Ni, Cu, and Zn. During the past 50 m.y. all of these elements accumulated over the East Pacific Rise at rates nearly an order of magnitude higher than those at non-rise-crest sites. In addition, factor analysis indicates that some of this material is carried substantial distances to the west of the rise crest. Accumulation rates of Fe in basal metalliferous sediments indicate that the hydrothermal activity that supplied amorphous Fe oxides to the East Pacific Rise areas was most intense during middle Eocene and late Miocene to early Pliocene time.

Mean chemical characteristics and volcano signatures of ice cores from Belukha, the Everest and three Svalbard sites

Ice cores from outside the Greenland and Antarctic ice sheets are difficult to date because of seasonal melting and multiple sources (terrestrial, marine, biogenic and anthropogenic) of sulfates deposited onto the ice. Here we present a method of volcanic sulfate extraction that relies on fitting sulfate profiles to other ion species measured along the cores in moving windows in log space. We verify the method with a well dated section of the Belukha ice core from central Eurasia. There are excellent matches to volcanoes in the preindustrial, and clear extraction of volcanic peaks in the post-1940 period when a simple method based on calcium as a proxy for terrestrial sulfate fails due to anthropogenic sulfate deposition. We then attempt to use the same statistical scheme to locate volcanic sulfate horizons within three ice cores from Svalbard and a core from Mount Everest. Volcanic sulfate is <5% of the sulfate budget in every core, and differences in eruption signals extracted reflect the large differences in environment between western, northern and central regions of Svalbard. The Lomonosovfonna and Vestfonna cores span about the last 1000 years, with good extraction of volcanic signals, while Holtedahlfonna which extends to about AD1700 appears to lack a clear record. The Mount Everest core allows clean volcanic signal extraction and the core extends back to about AD700, slightly older than a previous flow model has suggested. The method may thus be used to extract historical volcanic records from a more diverse geographical range than hitherto.

Abundance and chemical and mineral compositions of nodules from the Pacific Ocean

The monograph highlights extensive materials collected during expeditions of P.P. Shirshov Institute of Oceanology. We consider facial conditions of nodule formation, regularities of their distribution, stratigraphic position, petrography, mineral composition, textures, geochemistry of nodules and hosting sediments. Origin of iron-manganese nodules in the Pacific Ocean is considered as well.

Some physical and chemical proceddes in fluids

The ability to reproduce reduced gravity conditions for long periods is one of the reasons why the orbiting laboratory is so attractive. In this paper several fluid dynamics problem areas are reviewed in which zero-gravity conditions are of great importance. Although emphasis is placed on space processing, there are some older problems also in which gravity masks the phenomcna, impeding a reasonably simple approach to the solution. Three problems are considered: Thermal convection under reduced gravity. The dumping effect ofsurface gravity waves at the outset of convection induced by surface tractions is discussed in particular. The existence of convection is of concern for some satellite thermal control techniques presently used, and for most of the proposed manufacturing processes. Whereas convection should be normally avoided, problems related to the containerless stirring ofa melt constitute an exception. Secondly, gravity and chemical reactions. Although chemical reactions are independent of gravity because of the small mass of the molecules and atoms involved, in many cases the reaction rate dcpends on the arrival of the species to the reaction zone. When the arrival process is buoyancy-controlled, the net specd of the reaction will be affected by the gravity. Thirdly, two-phase flows under reduced gravity provkle interesting problems from boiling heat transfer to degasslng of melts. This part of the paper deals only with the measurement of sound veiocity in a liquid containing bubbles. It is suggested that such measurements should be mude under reduced gravity to provide reliable residís.

Integrated luminescent chemical microsensors based on GaN LEDs for security applications using smartphones

Development of PCB-integrateable microsensors for monitoring chemical species is a goal in areas such as lab-on-a-chip analytical devices, diagnostics medicine and electronics for hand-held instruments where the device size is a major issue. Cellular phones have pervaded the world inhabitants and their usefulness has dramatically increased with the introduction of smartphones due to a combination of amazing processing power in a confined space, geolocalization and manifold telecommunication features. Therefore, a number of physical and chemical sensors that add value to the terminal for health monitoring, personal safety (at home, at work) and, eventually, national security have started to be developed, capitalizing also on the huge number of circulating cell phones. The chemical sensor-enabled “super” smartphone provides a unique (bio)sensing platform for monitoring airborne or waterborne hazardous chemicals or microorganisms for both single user and crowdsourcing security applications. Some of the latest ones are illustrated by a few examples. Moreover, we have recently achieved for the first time (covalent) functionalization of p- and n-GaN semiconductor surfaces with tuneable luminescent indicator dyes of the Ru-polypyridyl family, as a key step in the development of innovative microsensors for smartphone applications. Chemical “sensoring” of GaN-based blue LED chips with those indicators has also been achieved by plasma treatment of their surface, and the micrometer-sized devices have been tested to monitor O2 in the gas phase to show their full functionality. Novel strategies to enhance the sensor sensitivity such as changing the length and nature of the siloxane buffer layer are discussed in this paper.

The Phase Space as a New Representation of the Dynamical Behaviour of Temperature and Enthalpy in a Reefer monitored with a Multidistributed Sensors Network

The study of temperature gradients in cold stores and containers is a critical issue in the food industry for the quality assurance of products during transport, as well as forminimizing losses. The objective of this work is to develop a new methodology of data analysis based on phase space graphs of temperature and enthalpy, collected by means of multidistributed, low cost and autonomous wireless sensors and loggers. A transoceanic refrigerated transport of lemons in a reefer container ship from Montevideo (Uruguay) to Cartagena (Spain) was monitored with a network of 39 semi-passive TurboTag RFID loggers and 13 i-button loggers. Transport included intermodal transit from transoceanic to short shipping vessels and a truck trip. Data analysis is carried out using qualitative phase diagrams computed on the basis of Takens?Ruelle reconstruction of attractors. Fruit stress is quantified in terms of the phase diagram area which characterizes the cyclic behaviour of temperature. Areas within the enthalpy phase diagram computed for the short sea shipping transport were 5 times higher than those computed for the long sea shipping, with coefficients of variation above 100% for both periods. This new methodology for data analysis highlights the significant heterogeneity of thermohygrometric conditions at different locations in the container.