Tying Spitzer’s IRS Calibration to IRAC: Observations of IRS Standard Stars
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Kathleen E. Kraemer↗
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Reconceptualizing the Ir III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor
Dual Ir III /L n Ni II metallaphotoredox catalyzed C(sp 3 )–C(sp 2 ) cross-coupling reactions are widely assumed to proceed by photoinduced single electron transfer steps due to the highly oxidizing Ir III * excited state (Ir III = [Ir(dF(CF 3 )ppy) 2 (dtbbpy)] + [PF 6 ] – ; dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; L n = dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Using time-resolved absorption and emission spectroscopy, we reveal that energy transfer between Ir III * and various LnNi II precatalysts and intermediates with k q ≥ 10 8 M –1 s –1 also drives catalysis. Specifically, the excited states of L n Ni II dihalide precatalysts/organometallic intermediates accessible by energy transfer appear to drive bond homolysis, halogen radical elimination, and reductive elimination reactions that facilitate formation of cross-coupled products. Energy transfer dynamics consequently circumvent the need for photoinduced electron transfer, thereby extending substrate scopes to coupling partners that cannot be oxidized by Ir III *. Within a cross-electrophile coupling model reaction between 4-bromobenzotrifluoride and bromocyclohexane, energy transfer activates the L n Ni II precatalyst at early reaction times before nucleophilic reductants are present. In the absence of Ir III , direct excitation of L n Ni II (Br) 2 also activates the precatalyst to form a L n Ni II (Br)(Aryl) intermediate. To compare energy transfer and electron transfer kinetics, we determined rate constants for reductive quenching by Br – (k SET = 4.1 × 10 8 M –1 s –1 ) and for the subsequent electron transfer from reduced Ir III•– to L n Ni II (Br) 2 (k SET = 4.1 × 10 7 M –1 s –1 ) using Stern-Volmer analysis and pulse radiolysis, respectively. Energy transfer rate constants are competitive with the electron transfer rate constants and energy transfer is a parallel pathway within metallaphotoredox catalysis. Exploiting the energy transfer mechanism, we demonstrate highly selective cross-electrophile coupling between 4-chlorobenzotrifluoride and bromocyclohexane to form exclusively cross-coupled product. Here, with alkyl-trifluoroborate nucleophiles that do not reductively quench IrIII* emission, transmetalation with L n Ni II (Br/Cl)(Aryl) followed by energy transfer also drives excited state reductive elimination to form C(sp 3 )–C(sp 2 ) cross-coupled product. Similarly, energy transfer rather than Ni II oxidation drives C(sp 2 )–OR reductive elimination, despite the strongly oxidizing ability of Ir III *. In total, these reactions demonstrate energy transfer processes from Ir III * to L n Ni II in metallaphotoredox catalysis that can unlock alternative reactive pathways.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Discovery of a compact far-infrared source, IR 12.4+0.5
Results are reported for far-IR, CO, 8-GHz, 15-GHz, H2O, and near-IR observations of a compact far-IR source (designated IR 12.4+0.5) in the M17 molecular cloud, as well as for CO and near-IR observations of a CO peak (designated MC 12.8+0.5) 24 arcmin to the NE of IR 12.4+0.5. The observed far-IR signal from IR 12.4+0.5 is found to correspond to a flux of 2400 Jy at 69 microns for a color temperature of 70 K, and the FWHM size of the source is estimated to be about 36 arcsec. The CO data for both sources and the observed reddening of background giants are shown to indicate high column densities; the existence of internal heat sources is inferred from the measured CO temperatures and the far-IR emission. It is concluded that the two sources are probably sites of very recent or ongoing star formation and that IR 12.4+0.5 is consistent with the 'cocoon star' model of early star formation.
Wright, E. L.↗
Infrared Camera System for Visualization of IR-Absorbing Gas Leaks
Leak detection and location remain a common problem in NASA and industry, where gas leaks can create hazardous conditions if not quickly detected and corrected. In order to help rectify this problem, this design equips an infrared (IR) camera with the means to make gas leaks of IR-absorbing gases more visible for leak detection and location. By comparing the output of two IR cameras (or two pictures from the same camera under essentially identical conditions and very closely spaced in time) on a pixel-by-pixel basis, one can cancel out all but the desired variations that correspond to the IR absorption of the gas of interest. This can be simply done by absorbing the IR lines that correspond to the gas of interest from the radiation received by one of the cameras by the intervention of a filter that removes the particular wavelength of interest from the "reference" picture. This can be done most sensitively with a gas filter (filled with the gas of interest) placed in front of the IR detector array, or (less sensitively) by use of a suitable line filter in the same location. This arrangement would then be balanced against the unfiltered "measurement" picture, which will have variations from IR absorption from the gas of interest. By suitable processing of the signals from each pixel in the two IR pictures, the user can display only the differences in the signals. Either a difference or a ratio output of the two signals is feasible. From a gas concentration viewpoint, the ratio could be processed to show the column depth of the gas leak. If a variation in the background IR light intensity is present in the field of view, then large changes in the difference signal will occur for the same gas column concentration between the background and the camera. By ratioing the outputs, the same signal ratio is obtained for both high- and low-background signals, even though the low-signal areas may have greater noise content due to their smaller signal strength. Thus, one embodiment would use a ratioed output signal to better represent the gas column concentration. An alternative approach uses a simpler multiplication of the filtered signal to make the filtered signal equal to the unfiltered signal at most locations, followed by a subtraction to remove all but the wavelength-specific absorption in the unfiltered sample. This signal processing can also reveal the net difference signal representing the leaking gas absorption, and allow rapid leak location, but signal intensity would not relate solely to gas absorption, as raw signal intensity would also affect the displayed signal. A second design choice is whether to use one camera with two images closely spaced in time, or two cameras with essentially the same view and time. The figure shows the two-camera version. This choice involves many tradeoffs that are not apparent until some detailed testing is done. In short, the tradeoffs involve the temporal changes in the field picture versus the pixel sensitivity curves and frame alignment differences with two cameras, and which system would lead to the smaller variations from the uncontrolled variables.
Youngquist, Robert↗
Combined UV and IR Ozone Profile Retrieval from TROPOMI and CrIS Measurements
Vertical ozone profiles from combined spectral measurements in the ultraviolet and infrared spectral range were retrieved by using data from the TROPOspheric Monitoring Instrument on the Sentinel-5 Precursor (TROPOMI/S5P) and the Cross-track Infrared Sounder on the Suomi National Polar-orbiting Partnership (CrIS/Suomi-NPP), which are flying in loose formation 3 min apart in the same orbit. A previous study of ozone profiles retrieved exclusively from TROPOMI UV spectra showed that the vertical resolution in the troposphere is clearly limited (Mettig et al., 2021). The vertical resolution and the vertical extent of the ozone profiles is improved by combining both wavelength ranges compared to retrievals limited to UV or IR spectral data only. The combined retrieval particularly improves the accuracy of the retrieved tropospheric ozone and to a lesser degree stratospheric ozone up to 30 km. An increase in the degrees of freedom (DOF) by 1 DOF was found in the UV + IR retrieval compared to the UV-only retrieval. Compared to previous publications, which investigated combinations of UV and IR observations from the Ozone Monitoring Instrument and Tropospheric Emission Spectrometer (OMI and TES) and Global Ozone Monitoring Experiment version 2 and Infrared Atmospheric Sounding Interferometer (GOME-2 and IASI) pairs, the degree of freedom is lower, which is attributed to the reduced spectral resolution of CrIS compared to TES or IASI. Tropospheric lidar and ozonesondes were used to validate the ozone profiles and tropospheric ozone content (TOC). In their comparison with tropospheric lidars, both ozone profiles and TOCs show smaller biases for the retrieved data from the combined UV + IR observation than from the UV observations alone. For the ozone profiles below 10 km, the mean differences are around ±10 % and the mean TOC varies around ±3 DU. We show that TOCs from the combined retrieval agree better with ozonesonde results at northern latitudes than the UV-only and IR-only retrievals and also have lower scatter. In the tropics, the IR-only retrieval shows the best agrement with TOCs derived from ozonesondes. While in general the TOCs show good agreement with ozonesonde data, the profiles have a positive bias of around 30 % between 10 and 15 km. The reason is probably a positive stratospheric bias from the IR retrieval. The comparison of the UV + IR and UV ozone profiles up to 30 km with the Microwave Limb Sounder (MLS) demonstrates the improvement of the UV + IR profile in the stratosphere above 18 km. In comparison to the UV-only approach the retrieval shows improvements of up to 10 % depending on latitude but can also show worse results in some regions and latitudes.
Ozone↗
Mineralogy and Thermal Properties of V-Type Asteroid 956 Elisa: Evidence for Diogenitic Material from the Spitzer IRS (5-35 Micrometers) Spectrum
We present the thermal infrared (5-35 micrometer) spectrum of 956 Elisa as measured by the Spitzer Infrared Spectrograph ("IRS"; Houck,1.R. et .11. [20041. Astrophys, 1. SuppL 154, 18-24) together with new ground-based lightcurve data and near-IR spectra. From the visible lightcurve photometry, we determine a rotation period of 16.494 +/- 0.001 h, identify the rotational phase of the Spitzer observations, and estimate the visible absolute magnitude (Hv) at that rotational phase to be 12.58 +/- 0.04. From radiometric analysis of the thermal flux spectrum, we find that at the time of observation 956 Elisa had a projected radius of 5.3 +/- 0.4 km with a visible albedo pv = 0.142+/- 0.022, significantly lower than that of the prototype V-type asteroid, 4 Vesta. (This corresponds to a radius of 5.2 +/- 0.4 km at lightcurve mean.) Analysis with the standard thermal model (STM) results in a sub-solar temperature of 292.3 +/- 2.8 K and beaming parameter eta = 1.16 +/- 0.05. Thermophysical modeling places a lower limit of 20 J m(exp -2)K(exp -1)s(exp -1/2) on the thermal inertia of the asteroid's surface layer (if the surface is very smooth) but more likely values fall between 30 and 150 J m(exp -2)K(exp -1)s(exp -1/2) depending on the sense of rotation. The emissivity spectrum, calculated by dividing the measured thermal flux spectrum by the modeled thermal continuum, exhibits mineralogically interpretable spectral features within the 9-12 micrometer reststrahlen band, the 15-16.5 micrometer Si-O-Si stretching region, and the 16-25 micrometer reststrahlen region that are consistent with pyroxene of diogenitic composition: extant diogenitic pyroxenes fall within the narrow compositional range W0(sub 2+/-1)En(sub 74+/-2)Fs(sub 24+/-1). Spectral deconvolution of the 9-12 micrometer reststrahlen features indicates that up to approximately 20% olivine may also be present, suggesting an olivine-diogenite-like mineralogy. The mid-IR spectrum is inconsistent with non-cumulate eucrite as the major component on the surface of 956 Elisa, although cumulate eucrite material may be present at abundances lower than that of the diogenite component. Analysis of new near-IR spectra of 956 Elisa with the Modified Gaussian Model (MGM; Sunshine, J,M., Pieters, C.M., Pratt, S.F.[1990]. J. Geophys. Res, 95 (May), 6955-6966) results in two pyroxene compositions: 75% magnesian low-Ca pyroxene and 25% high-Ca pyroxene. High-Ca pyroxene is not evident in the mid-IR data, but may belong to a component that is underrepresented in the mid-IR spectrum either because of its spatial distribution on the asteroid or because of its particle size. High-Ca pyroxenes that occur as exsolution lamellae may also be more evident spectrally in the NIR than in the mid-IR. In any case, we find that the mid-IR spectrum of 956 Elisa is dominated by emission from material of diogenite- like composition, which has very rarely been observed among asteroids.
Lim, Lucy F.↗
Calibrating Historical IR Sensors Using GEO, and AVHRR Infrared Tropical Mean Calibration Models
Long-term, remote-sensing-based climate data records (CDRs) are highly dependent on having consistent, wellcalibrated satellite instrument measurements of the Earth's radiant energy. Therefore, by making historical satellite calibrations consistent with those of today's imagers, the Earth-observing community can benefit from a CDR that spans a minimum of 30 years. Most operational meteorological satellites rely on an onboard blackbody and space looks to provide on-orbit IR calibration, but neither target is traceable to absolute standards. The IR channels can also be affected by ice on the detector window, angle dependency of the scan mirror emissivity, stray-light, and detector-to-detector striping. Being able to quantify and correct such degradations would mean IR data from any satellite imager could contribute to a CDR. Recent efforts have focused on utilizing well-calibrated modern hyper-spectral sensors to intercalibrate concurrent operational IR imagers to a single reference. In order to consistently calibrate both historical and current IR imagers to the same reference, however, another strategy is needed. Large, well-characterized tropical-domain Earth targets have the potential of providing an Earth-view reference accuracy of within 0.5 K. To that effort, NASA Langley is developing an IR tropical mean calibration model in order to calibrate historical Advanced Very High Resolution Radiometer (AVHRR) instruments. Using Meteosat-9 (Met-9) as a reference, empirical models are built based on spatially/temporally binned Met-9 and AVHRR tropical IR brightness temperatures. By demonstrating the stability of the Met-9 tropical models, NOAA-18 AVHRR can be calibrated to Met-9 by matching the AVHRR monthly histogram averages with the Met-9 model. This method is validated with ray-matched AVHRR and Met-9 biasdifference time series. Establishing the validity of this empirical model will allow for the calibration of historical AVHRR sensors to within 0.5 K, and thereby establish a climate-quality IR data record.
Scarino, Benjamin↗
In-situ polarization modulation IRRAS investigation of ammonia electrooxidation on Pt-Ir and Pt-Ru nanoparticles prepared on engineered catalyst supports
The catalytic activity and surface reactivity of monometallic Pt and bimetallic Pt-Ir and Pt-Ru nanoparticles, supported on two distinct Engineered Catalyst Supports (ECSs), were investigated for the Ammonia Electrooxidation Reaction (AmER) in alkaline media. XRD measurements confirmed alloy formation between Pt-Ir and Pt-Ru nanoparticles, as indicated by the shift of the (111) reflection to higher 2θ values. Cyclic voltammetry, linear sweep voltammetry, and chronoamperometry experiments were conducted to assess the catalytic activity of the Pt, Pt-Ir, and Pt-Ru electrocatalysts. All bimetallic catalysts exhibited lower onset potentials compared to Pt. The differing Tafel slopes between Pt (74 mV dec⁻¹), Pt-Ir (152 mV dec⁻¹), and Pt-Ru (118–197 mV dec⁻¹) suggest that alloying Pt with Ir or Ru alters the reaction mechanisms. Furthermore, the bimetallic Pt-Ir and Pt-Ru catalysts demonstrated greater tolerance for concentrated ammonia solutions relative to Pt. In-situ Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) provided insights into the formation of N-H species, azide anions (N₃⁻), and N-O compounds. For the Pt-Ru catalyst, an additional peak around ~3600 cm⁻¹ was observed, corresponding to OH⁻ species. The PM-IRRAS results align with the Gerischer–Mauerer mechanism, indicating that partially dehydrogenated ammonia adsorbates act as active intermediates in the oxidation of ammonia over Pt-Ir and Pt-Ru catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ir(hkl) Surface Electrochemistry in a Nonadsorbing Acidic Medium
The fundamental properties of electrochemical materials depend on the multiple and often complex interactions between electrode surface sites and electrolyte species at the electrochemical interface. Despite Iridium use in electrolyzer systems, much of its surface electrochemistry remains underexplored. This study investigates the surface electrochemistry of Ir(111), Ir(100), and Ir(110) surfaces in acidic media. Using cyclic voltammetry and CO charge displacement experiments, we establish the charge states and adsorbate coverages as a function of the electrode potential, revealing the presence of hydrogen and hydroxyl co-adsorption at low potentials on (111), and almost no coverage of H ad on (110) facet. In situ Shell Isolated Nanoparticle Enhanced Raman Spectroscopy experiments provide direct evidence of the formation of key adsorbate species, such as hydrogen, hydroxyl, and oxygen, but most importantly, their interactions with interfacial water, confirmed by Density Functional Theory calculations. Our findings highlight the role of co-adsorption and interspecies interactions, with microkinetic adsorption voltammetry simulations corroborating the influence of lateral interactions on adsorption dynamics, particularly for Ir(100) where the OHad formation occurs as a sharp adsorption/desorption current. Our results underscores the importance of interfacial water and hydrogen bonding networks in shaping the electrochemical behavior on Ir surfaces, refining our baseline understanding of the Ir surface electrochemistry necessary for the development of advanced Ir-based electrochemical materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Olefin Coupling Catalyzed by (Pybox)Os Complexes via Osmacyclopentane Intermediates: Comparison with Isoelectronic (Phebox)Ir
(Pybox)Os is found to catalyze alkene hydrovinylation, effecting the dimerization of ethylene, tail-to-tail coupling of propene and 1-butene, and cross-coupling of ethylene with higher α-olefins. This reactivity contrasts with the previously reported dehydrogenative coupling of ethylene to give butadiene catalyzed by the isoelectronic fragment (Phebox)Ir. The reaction mechanism was investigated through computational and experimental means. Both the Os- and Ir-catalyzed reactions proceed through a [2 + 2 + 1] cyclization of the corresponding bis-olefin complex to yield an experimentally observed metallacyclopentane intermediate. In both cases, the metallacyclopentane undergoes β- H elimination, via a dechelated κ 2 -pincer-ligated intermediate, to yield a σ−π-but-3-enyl hydride complex or derivative. Both the greater reactivity and the distinct chemoselectivity of the Os system relative to the Ir system are attributable to C−H reductive elimination by the σ−π-but-3-enyl hydride having a barrier for Os much lower than that for Ir. This lower barrier to C−H elimination for Os is unexpected given that the thermodynamic driving force for elimination is much less for Os than for Ir. Computational studies of model complexes were conducted, comparing (Pybox)Os(L)(CH 3 )(H) with the isoelectronic (Phebox)Ir(L)(CH 3 )(H). The results indicate that the more facile kinetics with Os relative to Ir may be general for C−H elimination from six-coordinate d 6 complexes of the two metals, as well as for the microscopic reverse, i.e., C−H addition to the corresponding four-coordinate d 8 species.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
An obscured quasar census with the 4MOST IR AGN survey: design, predicted properties, and scientific goals
ABSTRACT We present the 4MOST (4-metre Multi-Object Spectroscopic Telescope) infrared (IR) AGN survey, the first large-scale optical spectroscopic survey characterizing mid-infrared (MIR) selected obscured active galactic nuclei (AGNs). The survey targets $\approx 212\,000$ obscured IR AGN candidates over $\approx 10\,000 \rm \: deg^2$ down to a magnitude limit of $r_{\rm AB}=22.8 \, \rm mag$ and will be $\approx 100 \times$ larger than any existing obscured IR AGN spectroscopic sample. We select the targets using an MIR colour criterion applied to the unWISE catalogue from the WISE (Wide-field Infrared Survey Explorer) all-sky survey, and then apply a $r-W2\ge 5.9 \rm \: mag$ cut; we demonstrate that this selection will mostly identify sources obscured by $N_{\rm H}>10^{22} \rm \: cm^{-2}$. The survey complements the 4MOST X-ray survey, which will follow up $\sim 1\,\rm M$ eROSITA (extended ROentgen Survey with an Imaging Telescope Array)-selected (typically unobscured) AGN. We perform simulations to predict the quality of the spectra that we will obtain and validate our MIR–optical colour-selection method using X-ray spectral constraints and UV-to-far-IR spectral energy distribution (SED) modelling in four well-observed deep-sky fields. We find that: (1) $\approx 80-87{{\ \rm per\ cent}}$ of the WISE-selected targets are AGN down to $r_{\rm AB}=22.1-22.8 \: \rm mag$ of which $\approx 70{{\ \rm per\ cent}}$ are obscured by $N_{\rm H}>10^{22} \: \rm cm^{-2}$, and (2) $\approx 80{{\ \rm per\ cent}}$ of the 4MOST IR AGN sample will remain undetected by the deepest eROSITA observations due to extreme absorption. Our SED-fitting results show that the 4MOST IR AGN survey will primarily identify obscured AGN and quasars ($\approx 55{{\ \rm per\ cent}}$ of the sample is expected to have $L_{\rm AGN,IR}>10^{45} \rm \: erg \: s^{-1}$) residing in massive galaxies ($M_{\star }\approx 10^{10}-10^{12} \rm \: M_{\odot }$) at $z\approx 0.5-3.5$ with $\approx 33{{\ \rm per\ cent}}$ expected to be hosted by starburst galaxies.
Andonie, Carolina (ORCID:0000000255804298)↗
The bow shock structure of IRS 7 - Wind-wind collision near the Galactic center
New structural details of ionized gas associated with IRS 7, a mass-losing supergiant near the Galactic center, are reported, and radio continuum and theoretical maps are compared. High-resolution multiconfiguration VLA observations of IRS 7 reveal ionized gas with a bow shock structure at a wavelength of 2 cm. The apex of the bow shock is facing more toward the cluster of blue stellar objects, known as IRS 16, than Sgr A*, the compact nonthermal source near the Galaxy's dynamical center. It is inferred that the shape of the mass-losing envelope of IRS 7 is influenced by Galactic winds from IRS 16. It is concluded from a comparison of the morphology of the ionized envelope of IRS 7 with simple theoretical modeling of the bow shock structure that the shape of the shock results from the collision between the Galactic center and stellar winds rather than from the motion of IRS 7 through the interstellar medium.
Yusef-Zadeh, Farhad↗
Visualizing Infrared (IR) Spectroscopy with Computer Animation
IR Tutor, an interactive, animated infrared (IR) spectroscopy tutorial has been developed for Macintosh and IBM-compatible computers. Using unique color animation, complicated vibrational modes can be introduced to beginning students. Rules governing the appearance of IR absorption bands become obvious because the vibrational modes can be visualized. Each peak in the IR spectrum is highlighted, and the animation of the corresponding normal mode can be shown. Students can study each spectrum stepwise, or click on any individual peak to see its assignment. Important regions of each spectrum can be expanded and spectra can be overlaid for comparison. An introduction to the theory of IR spectroscopy is included, making the program a complete instructional package. Our own success in using this software for teaching and research in both academic and industrial environments will be described. IR Tutor consists of three sections: (1) The 'Introduction' is a review of basic principles of spectroscopy. (2) 'Theory' begins with the classical model of a simple diatomic molecule and is expanded to include larger molecules by introducing normal modes and group frequencies. (3) 'Interpretation' is the heart of the tutorial. Thirteen IR spectra are analyzed in detail, covering the most important functional groups. This section features color animation of each normal mode, full interactivity, overlay of related spectra, and expansion of important regions. This section can also be used as a reference.
Charles B. Abrams↗
An Intercomparison Between Radar Reflectivity and the IR Cloud Classification Technique for the TOGA-COARE Area
Satellite infrared (IR) and visible (VIS) images from the Tropical Ocean Global Atmosphere - Coupled Ocean Atmosphere Response Experiment (TOGA-COARE) experiment are investigated through the use of Clustering Analysis. The clusters are obtained from the values of IR and VIS counts and the local variance for both channels. The clustering procedure is based on the standardized histogram of each variable obtained from 179 pairs of images. A new approach to classify high clouds using only IR and the clustering technique is proposed. This method allows the separation of the enhanced convection in two main classes: convective tops, more closely related to the most active core of the storm, and convective systems, which produce regions of merged, thick anvil clouds. The resulting classification of different portions of cloudiness is compared to the radar reflectivity field for intensive events. Convective Systems and Convective Tops are followed during their life cycle using the IR clustering method. The areal coverage of precipitation and features related to convective and stratiform rain is obtained from the radar for each stage of the evolving Mesoscale Convective Systems (MCS). In order to compare the IR clustering method with a simple threshold technique, two IR thresholds (Tir) were used to identify different portions of cloudiness, Tir=240K which roughly defines the extent of all cloudiness associated with the MCS, and Tir=220K which indicates the presence of deep convection. It is shown that the IR clustering technique can be used as a simple alternative to identify the actual portion of convective and stratiform rainfall.
Carvalho, L. M. V.↗
The Disposition of Pt, Pd, Ir, Os, and Ru in Marine Sediments and the K/T Boundary
The marine record of platinum group elements (PGEs) and Os isotopic compositions provides information on different inputs of PGEs into the oceans. Some studies based on a smaller subset of the PGEs suggest that the PGEs may suffer post-depositional mobility during diagenesis. In some K/T boundary clays, Kyte and others showed that the relative abundances of Pt, Pd, Ir, and Os can differ significantly from chondritic, which is the signature expected from fallout of the meteorite impact. In some K/T boundary sections, elevated Ir concentrations are observed as far as 1 meter from the cm-thick boundary clay containing the meteoritic ejecta. The purpose of this study was to characterize Pt, Pd, Ir, Os, and Ru abundances in zones including the K/T boundary. We determined PGE abundances of boundary clays at two hemipelagic sites (Stevns Klint, Denmark and Caravaca, Spain) in which previous studies by Kyte and others showed that the Ir anomaly is confined to within a few cm. We also analyzed two pelagic Pacific sites: a boundary clay from the north Pacific (Hole 465A) characterized by a 0.5 m thick Ir anomaly and a transect across the K/T boundary from the south Pacific (Hole 596) where the Ir anomaly spans 2 m. The Stevns Klint, Caravaca, and north Pacific sites are characterized by abundant marls and limestones in the section, whereas the south Pacific site is dominated by clays. Samples were spiked with isotopic tracers, mixed with a flux, S and Ni, and equilibrated by fusion. PGEs were extracted from the Ni and analyzed on a Finnigan Element ICP-MS. We find that the narrow Caravaca and Stevns Klint boundary clays have relative PGE abundance patterns indistinguishable from chondritic values. The two Pacific sites were found to have nearly identical PGE patterns but have ratios at the peak, which differ from chondritic values as found earlier by Evans et al. The Pacific sites were found to have nearly identical PGE patterns but are extremely depleted in OS (Os/Ir = 0.07-0.15) and slightly enriched in Pd and Pt relative to Ir.
Lee, Cin-Ty↗
Ramification of complex magnetism in Nd 2 Ir 2 O 7 observed by Raman scattering spectroscopy
Using Raman scattering spectroscopy, we uncover a complex magnetic behavior of Nd2Ir2O7, which stands out among magnetic pyrochlores by the lowest temperature of the all-in-all-out (AIAO) Ir moments ordering (${T}_{{\rm{Ir}}}^{{\rm{N}}} = 33$ K) and the highest temperature at which AIAO order of rare-earth Nd ions is detected (${T}_{{\rm{Nd}}}^{{\rm{* }}}$ = 15 K). Detected magnetic Raman scattering and calculations of expected response allow us to demonstrate that the ordering of Ir magnetic moments is accompanied by an appearance of one-magnon Raman modes at 26.3 and 29.6 meV compatible with the AIAO order and allowing to estimate the energies of Ir-Ir interactions. An additional two-magnon excitation of the AIAO Nd order at around 33 meV appears in the spectra below the ordering temperature of Nd moments ${T}_{{\rm{Nd}}}^{{\rm{* }}}$ = 15 K. In the temperature range between 15 K and 33 K we observe a broad mode, which demonstrates strong temperature dependence and shifts on cooling below 20 K from 14 meV to higher frequencies, and disappears at 5 K, when two-magnon excitation of Nd moments becomes prominent. We suggest an interpretation of this excitation in terms of continuum arising from collective fluctuations of Nd moments above the transition. This complex behavior emerges from the interplay of strong spin-orbit coupling, electronic correlations, and geometric frustration on two magnetic pyrochlore sublattices of Nd and Ir ions.
magnetic properties and materials↗
Future development of IR thermovision weather satellite equipment
The self radiation of the surface being viewed is used for image synthesis in IR thermovision equipment. The installation of such equipment aboard weather satellites makes it possible to obtain cloud cover pictures of the earth's surface in a complete orbit, regardless of the illumination conditions, and also provides quantitative information on the underlying surface temperature and cloud top height. Such equipment is used successfully aboard the Soviet satellites of the Meteor system, and experimentally on the American satellites of the Nimbus series. With regard to surface resolution, the present-day IR weather satellite equipment is inferior to the television equipment. This is due primarily to the comparatively low detectivity of the IR detectors used. While IR equipment has several fundamental advantages in comparison with the conventional television equipment, the problem arises of determining the possibility for future development of weather satellite IR thermovision equipment. Criteria are examined for evaluating the quality of IR.
Listratov, A. V.↗
Measurement and analysis of distribution coefficients in Fe-Ni alloys containing S and/or P. II - K(Ir), K(Ge), and K(Cu)
Crystals of Fe-Ni-S-P alloys containing Ir, Ge, and Cu in small amounts were grown by plane front solidification. The electron microprobe was used to measure the compositions of these alloys. The Ir, Ge, and Cu distribution coefficients were determined by an analytical procedure from the composition data. The distribution coefficients of Ir, Ge, and Cu vary from 1.20 to 11.0, 0.75 to 2.1, and 0.06 to 0.84, respectively. K(Ir) and K(Ge) increase and K(Cu) decreases with the S content of the liquid. K(Cu) increases and K(Ir) and K(Ge) decrease with the P content of the liquid. Mathematical expressions have been formulated to relate the Ir, Ge, and Cu distribution coefficients to the S and P contents of the liquid. These distribution coefficients are important to the study of the solidification behavior of iron meteorites.
Sellamuthu, R.↗