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Surface inspection using FTIR spectroscopy

The use of reflectance Fourier transform infrared (FTIR) spectroscopy as a tool for surface inspection is described. Laboratory instruments and portable instruments can support remote sensing probes that can map chemical contaminants on surfaces with detection limits under the best of conditions in the sub-nanometer range, i.e.. near absolute cleanliness, excellent performance in the sub-micrometer range, and useful performance for films tens of microns thick. Examples of discovering and quantifying contamination such as mineral oils and greases, vegetable oils, and silicone oils on aluminum foil, galvanized sheet steel, smooth aluminum tubing, and sandblasted 7075 aluminum alloy and D6AC steel. The ability to map in time and space the distribution of oil stains on metals is demonstrated. Techniques associated with quantitatively applying oils to metals, subsequently verifying the application, and non-linear relationships between reflectance and the quantity oil are described.

Powell, G. L.

FTIR studies of low temperature sulfuric acid aerosols

Sub-micrometer sized sulfuric acid H2SO4 particles were generated using a constant output atomizer source. The particles were then exposed to water vapor before being injected into a low temperature cell. Multipass transmission Fourier Transformation Infrared (FTIR) spectroscopy was used to determine the phase and composition of the aerosols as a function of time for periods of up to five hours. Binary H2SO4H2O aerosols with compositions from 35 to 95 wt % H2SO4 remained liquid for over 3 hours at room temperatures ranging from 189-240 K. These results suggest that it is very difficut to freeze SSAs via homogeneous nucleation. Attempts to form aerosols more dilute than 35 wt % H2SO4 resulted in ice formation.

Anthony, S. E.

FTIR Spectroscopy of HNO3 and NO2 Relevant to Stratospheric Wake Analysis

The Fourier Transform Infrared (FTIR) technique has been employed to measure absolute concentrations of nitric acid (HNO3) and nitrogen dioxide (NO2) with 1/cm resolution and an absorption pathlength of 4 m under quasi-static and flow conditions at atmospheric pressure and room temperature. Water features seen under quasi-static conditions diminished in intensity under flowing conditions. Nitric acid was observed in the 1660-1760/cm range, while nitrogen dioxide was detected both in the 1536-1660 and 1213-1400/cm ranges. Concentrations of nitrogen dioxide and nitric acid were determined to be 11.9 and 4.35 parts per million (ppm), respectively, with an uncertainty of 0.2 ppm. Experiments are underway with a 10 m cell to measure the absorption of nitric acid, water, sulfur dioxide, hydrochloric acid and ammonia on various materials such as glass, teflon, stainless steel and aluminum used for implementation of the flow system. Such materials will be used for the measurements of stratospheric trace gases by the Quartz Crystal Microbalance (QCM) and Surface Acoustic Wave (SAW) devices.

Abina, Rafiu A.

Retrieval of HCl and HNO3 Profiles from Ground-Based FTIR Data Using SFIT2

A recently developed algorithm, SFIT2, is used to assess profile information available in ground-based FTIR measurements of HCl and HNO3 and to analyze spectra recorded at Lauder, New Zealand, and Arrival Heights, Antarctica. It is shown that the altitude range of HCI retrievals may be extended by using multiple spectral lines. A preliminary analysis of a five year record of HNO3 at Lauder shows that the Pinatubo aerosol caused a large increase of HNO3 in a layer at about 20-30 km while having little effect at lower altitude.

Connor, Brian

Raman and FTIR Studies of Silicon Carbide Surface Damage from Palladium Implantation in Presence of Hydrogen

The ion implantation in a crystal such as silicon carbide will cause both damage in the ion track and in the substrate at the end of the ion track. We used both keV, and MeV Pd ions in fabricating electronic chemical sensors in silicon carbide, which can operate at elevated temperatures. In order to study the feasibility of fabricating an optical chemical sensor (litmus sensor), we need to understand the optical behavior of the embedded damage in the presence of hydrogen, as well as the potential chemical interaction of silicon carbide broken lattice bonds with the hydrogen dissociated from gas by palladium. Implanted samples of silicon carbide were studied using both Raman spectroscopy and FTIR (Fourier Transform-Infrared). The results of this work will be presented during the meeting.

Muntele, I.

In-situ micro-FTIR Study of Thermal Changes of Organics in Tagish Lake Meteorite: Behavior of Aliphatic Oxygenated Functions and Effects of Minerals

Systematic in-situ FTIR heating experiments of Tagish Lake meteorite grains have been performed in order to study thermal stability of chondritic organics. Some aliphatic model organic substances have also been used to elucidate effects of hydrous phyllosilicate minerals on the thermal stability of organics. The experimental results indicated that organic matter in the Tagish Lake meteorite might contain oxygenated aliphatic hydrocarbons which are thermally stable carbonyls such as ester and/or C=O in ring compounds. The presence of hydrous phyllosilicate minerals has a pronounced effect on the increase of the thermal stability of aliphatic and oxygenated functions. These oxygenated aliphatic organics in Tagish Lake can be formed during the aqueous alteration in the parent body and the formation temperature condition might be less than 200 C, based especially on the thermal stability of C-O components. The hydrous phyllosilicates might provide sites for organic globule formation and protected some organic decomposition

Kebukawa, Yoko

Spaceborne Hybrid-FPGA System for Processing FTIR Data

Progress has been made in a continuing effort to develop a spaceborne computer system for processing readout data from a Fourier-transform infrared (FTIR) spectrometer to reduce the volume of data transmitted to Earth. The approach followed in this effort, oriented toward reducing design time and reducing the size and weight of the spectrometer electronics, has been to exploit the versatility of recently developed hybrid field-programmable gate arrays (FPGAs) to run diverse software on embedded processors while also taking advantage of the reconfigurable hardware resources of the FPGAs.

Bekker, Dmitriy

FTIR Analysis of Aerogel Keystones from the Stardust Interstellar Dust Collector: Assessment of Terrestrial Organic Contamination and X-Ray Microprobe Beam Damage

The Stardust Interstellar Dust Collector (SIDC) was intended to capture and return contemporary interstellar dust. The approx.0.1 sq m collector was composed of aerogel tiles (85% of the collecting area) and aluminum foils and was exposed to the interstellar dust stream for a total exposure factor of 20 sq m day. The Stardust Interstellar Preliminary Examination (ISPE) is a consortium-based project to characterize the collection using nondestructive techniques. Sandford et al. recently assessed numerous potential sources of organic contaminants in the Stardust cometary collector. These contaminants could greatly complicate the analysis and interperetation of any organics associated with interstellar dust, particularly because signals from these particles are expected to be exceedingly small. Here, we present a summary of FTIR analyses of over 20 aerogel keystones, many of which contained candidates for interstellar dust.

Zolensky, M. E.

Water Content of the Oceanic Lithosphere at Hawaii from FTIR Analysis of Peridotite Xenoliths

Although water in the mantle is mostly present as trace H dissolved in minerals, it has a large influence on its melting and rheological properties. The water content of the mantle lithosphere beneath continents is better constrained by abundant mantle xenolith data than beneath oceans where it is mainly inferred from MORB glass analysis. Using Fourier transform infrared (FTIR) spectrometry, we determined the water content of olivine (Ol), clinopyroxene (Cpx) and orthopyroxene (Opx) in spinel peridotite xenoliths from Salt Lake Crater, Oahu, Hawaii, which are thought to represent fragments of the Pacific oceanic lithosphere that was refertilized by alkalic Hawaiian melts. Only Ol exhibits H diffusion profiles, evidence of limited H loss during xenolith transport to the surface. Water concentrations (Ol: 9-28 ppm H2O, Cpx: 246-566 ppm H2O, Opx: 116-224 ppm H2O) are within the range of those from continental settings but higher than those from Gakkel ridge abyssal peridotites. The Opx H2O contents are similar to those of abyssal peridotites from Atlantic ridge Leg 153 (170-230 ppm) but higher than those from Leg 209 (10- 14 ppm). The calculated bulk peridotite water contents (94 to 144 ppm H2O) are in agreement with MORB mantle source water estimates and lower than estimates for the source of Hawaiian rejuvenated volcanism (approx 540 ppm H2O) . The water content of Cpx and most Opx correlates negatively with spinel Cr#, and positively with pyroxene Al and HREE contents. This is qualitatively consistent with the partitioning of H into the melt during partial melting, but the water contents are too high for the degree of melting these peridotites experienced. Melts in equilibrium with xenolith minerals have H2O/Ce ratios similar to those of OIB

Peslier, Anne H.

Water Contents of the Mantle Beneath the Rio Grande Rift: FTIR Analysis of Kilbourne Hole Peridotite Xenoliths

Although nominally anhydrous mantle minerals contain only trace amounts of water, they are the main reservoir of water in the mantle. Added up at the scale of the Earth's mantle, these trace amounts of water represent oceans worth in mass]. Mantle xenoliths from Kilbourne Hole in southern New Mexico are ideal to study mantle water distribution in a rift tectonic setting as they come from a recently‐erupted maar in the middle of the Rio Grande Rift. Eleven lherzolites, one harzburgite, and one dunite are being analyzed for water contents by FTIR. The xenoliths will also be analyzed for major and trace element composition, Fe3+/Summation (Fe) ratios, and characterized petrologically. Olivines exhibit variable water contents with less water at the rims compared to the cores. This is probably due to H loss during decompression and xenolith transport by the host magma. Mantle water contents appear to have been primarily preserved in the core of the olivines, based on diffusion modeling of the typically plateau-shaped water content profiles across these grains. Water concentrations are in equilibrium between clino- and orthopyroxene, but olivine concentrations are typically not in equilibrium with those of either pyroxene. Lherzolites analyzed so far have water contents of 2‐12 ppm H2O in olivines, 125‐165 ppm H2O in orthopyroxenes, and 328‐447 ppm H2O in clinopyroxenes. These water contents are similar to, but with a narrower range, than those for the respective minerals in other continental peridotite xenoliths. The lherzolites have bulk-rock (BR) Al2O3 contents that range between 3.17 and 3.78 wt%, indicating similar degrees of partial melting, which could explain the narrow range of their pyroxene water contents. Primitive mantle normalized rare earth element (REE) profiles of the bulk lherzolites vary from light REE depleted to flat, with no significant differences between, nor relation to, their mineral water contents. Consequently, the metasomatic agents that enriched LREEs in these lherzolites were most likely water-poor. The harzburgite and the dunite have lower weight percent Al2O3 compared to the lherzolites (2.11% and 0.34% respectively) indicating higher degrees of melting. Their olivine water contents, however, are similar to those of the lherzolites. Moreover, no correlations are observed between pyroxene water contents and indices of melting or metasomatism between the lherzolite group, the harzburgite, and the dunite, although the latter has the lowest pyroxene water contents. More samples will be analyzed to determine if the water contents are controlled by melting, metasomatism, or a combination of the two in the Kilbourne Hole mantle.

Schaffer, Lillian A.

High Water Contents in the Siberian Cratonic Mantle: An FTIR Study of Udachnaya Peridotite Xenoliths

Water is believed to be a key factor controlling the long-term stability of cratonic lithosphere, but mechanisms responsible for the water content distribution in the mantle remain poorly constrained. Water contents were obtained by FTIR in olivine, pyroxene and garnet for 20 well-characterized peridotite xenoliths from the Udachnaya kimberlite (central Siberian craton) and equilibrated at 2-7 GPa. Water contents in minerals do not appear to be related to interaction with the host kimberlite. Diffusion modeling indicates that the core of olivines preserved their original water contents. The Udachnaya peridotites show a broad range of water contents in olivine (6.5 +/- 1.1 to 323 +- 65 ppm H2O (2 sigma)), and garnet (0 - 23 +/- 6 ppm H2O). The water contents of olivine and garnet are positively correlated with modal clinopyroxene, garnet and FeO in olivine. Water-rich garnets are also rich in middle rare earth elements. This is interpreted as the result of interaction between residual peridotites and water rich-melts, consistent with modal and cryptic metasomatism evidenced in the Siberian cratonic mantle. The most water-rich Udachnaya minerals contain 2 to 3 times more water than those from the Kaapvaal craton, the only craton with an intact mantle root for which water data is available. The highest water contents in olivine and orthopyroxene in this study (>= 300 ppm) are found at the bottom of the lithosphere (> 6.5 GPa). This is in contrast with the Kaapvaal craton where the olivines of peridotites equilibrated at > 6.4 GPa have < 1 ppm H2O. The latter "dry" olivine may make the base of the Kaapvaal cratonic root strong and thus protects it from erosion by the convective mantle The calculated viscosity for water-rich Udachnaya peridotites at > 6 GPa is lower or similar (8.4× 10(exp 16) to 8.0× 10(exp 18) Pa./s) to that of the asthenosphere (<= 3.7x10(exp 18) Pa./s ). Such lithologies would not be able to resist delamination by the convecting asthenosphere. However, seismology studies as well as the high equilibration pressures of our samples indicate that the Udachnaya cratonic lithosphere is 220-250 km thick. Consequently, the water-rich peridotites are likely not representative of the overall Siberian cratonic lithosphere. Their composition is linked to spatially limited melt metasomatism in mantle regions above asthenospheric upwellings responsible for the kimberlite magmatism prior to their ascent and eruption.

Doucet, Luc S.

Water Content in the SW USA Mantle Lithosphere: FTIR Analysis of Dish Hill and Kilbourne Hole Pyroxenites

Kilbourne Hole (NM, USA) and Dish Hill (CA, USA) mantle xenoliths sample continental mantle in two different tectonic settings. Kilbourne Hole (KH) is located in the Rio Grande rift. Dish Hill (DH) is located in the southern Mojave province, an area potentially affected by subduction of the Farallon plate beneath North America. FTIR analyses were obtained on well characterized pyroxenite, dunite and wehrlite xenoliths, thought to represent crystallized melts at mantle depths. PUM normalized REE patterns of the KH bulk-rocks are slightly LREE enriched and consistent with those of liquids generated by < 5% melting of a spinel peridotite source. Clinopyroxenes contain from 272 to 313 ppm weight H2O similar to the lower limit of KH peridotite clinopyroxenes (250-530 ppm H2O). This is unexpected as crystallized melts like pyroxenites should concentrate water more than residual mantle-like peridotites, given that H is incompatible. PUM normalized bulk REE of the DH pyroxenites are characterized by flat to LREE depleted REE profiles consistent with > 6% melting of a spinel peridotite source. Pyroxenite pyroxenes have no detectable water but one DH wehrlite, which bulk-rock is LREE enriched, has 4 ppm H2O in orthopyroxene and <1ppm in clinopyroxene. The DH pyroxenites may thus come from a dry mantle source, potentially unaffected by the subduction of the Farallon plate. These water-poor melts either originated from shallow oceanic lithosphere overlaying the Farallon slab or from continental mantle formed > 2 Ga. The Farallon subduction appears to have enriched in water the southwestern United States lithospheric mantle further east than DH, beneath the Colorado plateau.

Gibler, Robert

Constraining the Composition of the Subcontinental Lithospheric Mantle Beneath the East African Rift: FTIR Analysis of Water in Spinel Peridotite Mantle Xenoliths

The East African Rift System was initiated by the impingement of the Afar mantle plume on the base of the non-cratonic continental lithosphere (assembled during the Pan-African Orogeny), producing over 300,000 kmof continental flood basalts approx.30 Ma ago. The contribution of the subcontinental lithospheric mantle (SCLM) to this voluminous period of volcanism is implied based on basaltic geochemical and isotopic data. However, the role of percolating melts on the SCLM composition is less clear. Metasomatism is capable of hybridizing or overprinting the geochemical signature of the SCLM. In addition, models suggest that adding fluids to lithospheric mantle affects its stability. We investigated the nature of the SCLM using Fourier transform infrared spectrometry (FTIR) to measure water content in mantle xenoliths entrained in young (1 Ma) basaltic lavas from the Ethiopian volcanic province. The mantle xenoliths consist dominantly of spinel lherzolites and are composed of nominally anhydrous minerals, which can contain trace water as H in mineral defects. Eleven mantle xenoliths come from the Injibara-Gojam region and two from the Mega-Sidamo region. Water abundances of olivines in six samples are 1-5ppm H2O while the rest are below the limit of detection (<0.5 ppm H2O); orthopyroxene and clinopyroxene contain 80-238 and 111-340 ppm wt H2O, respectively. Two xenoliths have higher water contents - a websterite (470 ppm) and dunite (229 ppm), consistent with involvement of ascending melts. The low water content of the upper SCLM beneath Ethiopia is as dry as the oceanic mantle except for small domains represented by percolating melts. Consequently, rifting of the East African lithosphere may not have been facilitated by a hydrated upper mantle.

Erickson, Stephanie Gwen

Mantle Water Contents Beneath the Rio Grande Rift (NM, USA): FTIR Analysis of Rio Puerco and Kilbourne Hole Peridotite Xenoliths

Peridotite xenoliths from the Rio Grande Rift (RGR) are being analyzed for H (sub 2) O contents by FTIR (Fourier Transform Infrared) as well as for major and trace element compositions. Nine samples are from the Rio Puerco Volcanic Field (RP) which overlaps the central RGR and southeastern Colorado Plateau; seventeen samples are from Kilbourne Hole (KH) in the southern RGR. Spinel Cr# (Cr/(Cr+Al)) (0.08-0.46) and olivine Mg# (Mg/(Mg plus Fe)) (0.883-0.911) of all RGR samples fall within the olivine-spinel mantle array from [1], an indicator that peridotites are residues of partial melting. Pyroxene H (sub 2) O in KH correlate with bulk rock and pyroxene Al (sub 2) O (sub 3).The KH clinopyroxene rare earth element (REE) variations fit models of 0-13 percent fractional melting of a primitive upper mantle. Most KH peridotites have bulk-rock light REE depleted patterns, but five are enriched in light REEs consistent with metasomatism. Variation in H (sub 2) O content is unrelated to REE enrichment. Metasomatism is seen in RP pyroxenite xenoliths [2] and will be examined in the peridotites studied here. Olivine H (sub 2) O contents are low (less than or equal to 15 parts per million), and decrease from core to rim within grains. This is likely due to H loss during xenolith transport by the host magma [3]. Diffusion models of H suggest that mantle H (sub 2) O contents are still preserved in cores of KH olivine, but not RP olivine. The average H (sub 2) O content of Colorado Plateau clinopyroxene (670 parts per million) [4] is approximately 300 parts per million higher than RGR clinopyroxene (350 parts per million). This upholds the hypothesis that hydration-induced lithospheric melting occurred during flat-slab subduction of the Farallon plate [5]. Numerical models indicate hydration via slab fluids is possible beneath the plateau, approximately 600 kilometers from the paleo-trench, but less likely approximately 850 kilometers away beneath the rift [6].

Schaffer, L. A.

Water in the Lithospheric Mantle Beneath a Phanerozoic Continental Belt: FTIR Analyses of Alligator Lake Xenoliths (Yukon, Canada)

Water in the mantle influences melting, metasomatism, viscosity and electrical conductivity. The Alligator Lake mantle xenolith suite is one of three bimodal peridotite suites from the northern Canadian Cordillera brought to the surface by alkali basalts, i.e., it consists of chemically distinct lherzolites and harzburgites. The lherzolites have equilibration temperatures about 50 C lower than the harzburgites and are thought to represent the fertile upper mantle of the region. The harzburgites might have come from slightly deeper in the mantle and/or be the result of a melting event above an asthenospheric upwelling detected as a seismic anomaly at 400-500 km depth. Major and trace element data are best interpreted as the lherzolite mantle having simultaneously experienced 20-25% partial melting and a metasomatic event to create the harzburgites. Well-characterized xenoliths are being analyzed for water by FTIR. Harzburgites contain 29-52 ppm H2O in orthopyroxene (opx) and (is) approximately140 ppm H2O in clinopyroxene (cpx). The lherzolites have H2O contents of 27-150 ppm in opx and 46-361 ppm in cpx. Despite correlating with enrichments in LREE, the water contents of the harzburgite pyroxenes are low relative to those of typical peridotite xenoliths, suggesting that the metasomatic agents were water-poor, contrarily to what has been suggested before. The water content of cpx is about double that of opx indicating equilibrium. Olivine water contents are low ((is) less than 5 ppm H2O) and out of equilibrium with those of opx and cpx, which may be due to H loss during xenolith ascent. This is consistent with olivines containing more water in their cores than their rims. Olivines exclusively exhibit water bands in the 3400-3000 cm-1 range, which may be indicative of a reduced environment.

Gelber, McKensie

Water and Metasomatism in the Slave Cratonic Lithosphere (Canada): An FTIR Study

Water in the mantle influences melting, viscosity, seismic velocity, and electrical conductivity. The role played by water in the long-term stabilization of cratonic roots is currently being debated. This study focuses on water contents of mantle minerals (olivine, pyroxene and garnet) from xenoliths found in kimberlites of the Archean Slave craton. 19 mantle xenoliths from central Lac de Gras, and 10 from northern Jericho were analyzed by FTIR for water, and their equilibration depths span the several compositional layers identified beneath the region. At both locations, the shallow peridotites have lower water contents in their olivines (11-30 ppm H2O) than those from the deeper layers (28-300 ppm H2O). The driest olivines, however, are not at the base of the cratonic lithosphere (>6 GPa) as in the Kaapvaal craton. Instead, the deepest olivines are hydrous (31-72 ppm H2O at Lac de Gras and 275 ppm H2O at Jericho). Correlations of water in clinopyroxene and garnet with their other trace element contents are consistent with water being added by metasomatism by melts resembling kimberlite precursors in the mantle approx.0.35 Ga ago beneath Lac de Gras. The northern Jericho xenoliths are derived from a region of the Slave craton that is even more chemically stratified, and was affected at depth by the 1.27 Ga Mackenzie igneous events. Metasomatism at Jericho may be responsible for the particularly high olivine water contents (up to 300 ppm H2O) compared to those at Lac de Gras, which will be investigated by acquiring trace-element data on these xenoliths. These data indicate that several episodes of metasomatic rehydration occurred in the deep part of the Slave craton mantle lithosphere, with the process being more intense in the northern part beneath Jericho, likely related to a translithospheric suture serving as a channel to introduce fluids and/or melts in the northern region. Consequently, rehydration of the lithosphere does not necessarily cause cratonic root delamination and these peridotites may represent localized metasomatic zones - the wall rocks to kimberlite magma passage.

Kilgore, McKensie

FTIR analysis of unaged encapsulants

Fourier transform infrared spectroscopy (FITR) analysis (in ATR mode) of unaged encapsulants (EVA, POE, EPE) from a commercial source.

characterization