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At least 91 records · Page 5

Salt Hydrate Eutectic Mixtures for Near-ambient Thermal Energy Storage Applications

In this work, we synthesized and characterized Na2SO4.10H2O – Na2CO3.10H2O eutectic salt hydrate phase change material (PCM) using Differential Scanning Calorimetry (DSC), Attenuated total reflectance infrared spectroscopy (ATR-IR), and X-ray Diffraction (XRD) techniques. The eutectic point of the PCM mixture was predicted based on binary eutectic effect and ion exchange theory. The XRD and ATR-IR results indicate that the eutectic PCM mixture was formed based on only physical mixing without chemical interaction. Moreover, DSC results showed that the eutectic concentration is 50wt% Na2SO4.10H2O – 50wt% Na2CO3.10H2O with melting temperature of 25.18°C and melting enthalpy of 187.46 J/g. Also, 78% of melting enthalpy was recoverable after 10 melt/freeze cycles. This eutectic mixture has the potential to be used in building thermal comfort applications.

Gluesenkamp, Kyle↗

Evaluating a New Homogeneous Total Ozone Climate Data Record from GOME/ERS-2, SCIAMACHY/Envisat, and GOME-2/MetOp-A

The European Space Agency's Ozone Climate Change Initiative (O3-CCI) project aims at producing and validating a number of high-quality ozone data products generated from different satellite sensors. For total ozone, the O3-CCI approach consists of minimizing sources of bias and systematic uncertainties by applying a common retrieval algorithm to all level 1 data sets, in order to enhance the consistency between the level 2 data sets from individual sensors. Here we present the evaluation of the total ozone products from the European sensors Global Ozone Monitoring Experiment (GOME)/ERS-2, SCIAMACHY/Envisat, and GOME-2/MetOp-A produced with the GOME-type Direct FITting (GODFIT) algorithm v3. Measurements from the three sensors span more than 16 years, from 1996 to 2012. In this work, we present the latest O3-CCI total ozone validation results using as reference ground-based measurements from Brewer and Dobson spectrophotometers archived at the World Ozone and UV Data Centre of the World Meteorological Organization as well as from UV-visible differential optical absorption spectroscopy (DOAS)/Système D′Analyse par Observations Zénithales (SAOZ) instruments from the Network for the Detection of Atmospheric Composition Change. In particular, we investigate possible dependencies in these new GODFIT v3 total ozone data sets with respect to latitude, season, solar zenith angle, and different cloud parameters, using the most adequate type of ground-based instrument. We show that these three O3-CCI total ozone data products behave very similarly and are less sensitive to instrumental degradation, mainly as a result of the new reflectance soft-calibration scheme. The mean bias to the ground-based observations is found to be within the 1 plus or minus 1 percent level for all three sensors while the near-zero decadal stability of the total ozone columns (TOCs) provided by the three European instruments falls well within the 1-3 percent requirement of the European Space Agency's Ozone Climate Change Initiative project.

Satellite sensors↗

Reshaping Light-Emitting Diodes To Increase External Efficiency

Light-emitting diodes (LEDs) reshaped, according to proposal, increasing amount of light emitted by decreasing fraction of light trapped via total internal reflection. Results in greater luminous output power for same electrical input power; greater external efficiency. Furthermore, light emitted by reshaped LEDs more nearly collimated (less diffuse). Concept potentially advantageous for conventional red-emitting LEDs. More advantageous for new "blue" LEDs, because luminous outputs and efficiencies of these devices very low. Another advantage, proposed conical shapes achieved relatively easily by chemical etching of semiconductor surfaces.

Rogowski, Robert↗

Estimation of porphyrin concentration in the kerogen fraction of shales using high-resolution reflectance spectroscopy

An interpretive model for estimating porphyrin concentration in bitumen and kerogen from spectral reaflectance data in the visible and near-ultraviolet region of the spectrum is derived and calibrated. Preliminary results obtained using the model are consistent with concentrations determined from the bitumen extract and suggest that 40 to 60 percent of the total porphyrin concentration remains in the kerogen after extraction of bitumen from thermally immature samples. The reflectance technique will contribute to porphyrin and kerogen studies and can be applied at its present level of development to several areas of geologic and paleo-oceanographic research.

Holden, Peter N.↗

How well is Martian ozone inferred with reflectance spectroscopy?

The Mariner 9 UV spectrometer scanned from 2100 to 3500 Angstroms in one of its two spectral channels every 3 seconds with a spectral resolution of 15 Angstroms and an effective field-of-view of approximately 300 km(exp 2). The only gaseous absorption in the 2000 to 3000 Angstrom region was assumed to come from the Hartley band system of ozone, and therefore the amount of ozone was inferred by fitting this absorption feature with laboratory data of ozone absorption. Mars O3 as inferred from these spectra shows strong seasonal and latitudinal variation, with column abundances ranging from 0.2 microns at equatorial latitudes to 60 microns over the northern winter polar latitudes. The detectability limit of the spectrometer was approximately 3 microns. I use a radiative transfer model based on the discrete ordinate method to calculate synthetic radiance spectra. When typical amounts of dust and cloud are present, significant underestimation of O3 occurs. A factor of 3 times as much O3 is needed to generate the same spectrum for cloudy, dusty atmospheres as for a clear atmosphere. If the scattering properties of Martian clouds and dust were well known, then their appearance would not be a problem, as a model would be capable of retrieving the O3 abundance. However, these properties are not well known, which raises doubts about the effectiveness of the current UV spectroscopy technique used to measure O3. Spatial and temporal variability in temperature and water vapor have been claimed to account for the scatter of the data points. However, water vapor is a small source of odd hydrogen in the winter polar atmosphere, and may not account for most of the variability. Masking by clouds and dust may also account for some of the observed O3 variability, because the nature and opacity of the clouds and dust in the polar hood change dramatically in latitude and even on a day-to-day basis. As the maximum O3 abundance resides near the surface, spacecraft must be able to observe through the entire cloud and dust abundance in order to actually see the total O3 column abundance. If reflectance spectroscopy is used, as on Mariner 9, then the cloud and the airborne dust must be traversed twice; first by the incoming solar flux down to the surface, and then once again upon reflection from the surface out to the spacecraft.

Lindner, Bernhard Lee↗

In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

We present a study of the lithium nickel manganese cobalt oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2 , NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Furthermore, our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.

25 ENERGY STORAGE↗

Investigating drivers of microbial activity and respiration in a forested bog

Northern peatlands store nearly one-third of terrestrial carbon (C) stocks while covering only 3% of the global landmass; nevertheless, the drivers of C cycling in these often-waterlogged ecosystems are different from those that control C dynamics in upland forested soils. To explore how multiple abiotic and biotic characteristics of bogs interact to shape microbial activity in a northern, forested bog, we added a labile C tracer ( 13 C-labeled starch) to in situ peat mesocosms and correlated heterotrophic respiration with natural variation in several microbial predictor variables, such as enzyme activity and microbial biomass, as well as with a suite of abiotic variables and proximity to vascular plants aboveground. We found that peat moisture content was positively correlated with respiration and microbial activity, even when moisture levels exceeded total saturation, suggesting that access to organic matter substrates in drier environments may be limiting for microbial activity. Proximity to black spruce trees decreased total and labile heterotrophic respiration. This negative relationship may reflect the influence of tree evapotranspiration and peat shading effects; i.e., microbial activity may decline as peat dries and cools near trees. Here, we isolated the response of heterotrophic respiration to explore the variation in, and interactions among, multiple abiotic and biotic drivers that influence microbial activity. This approach allowed us to reveal the relative influence of individual drivers on C respiration in these globally important C sinks.

59 BASIC BIOLOGICAL SCIENCES↗

In Liquid Infrared Scattering Scanning Near-Field Optical Microscopy for Chemical and Biological Nanoimaging

Imaging biological systems with simultaneous intrinsic chemical specificity and nanometer spatial resolution in their typical native liquid environment has remained a long-standing challenge. In this paper we demonstrate a general approach of chemical nanoimaging in liquid based on infrared scattering scanning near-field optical microscopy (IR $s$-SNOM). It is enabled by combining AFM operation in a fluid cell with evanescent IR illumination via total internal reflection, which provides spatially confined excitation for minimized IR water absorption, reduced far-field background, and enhanced directional signal emission and sensitivity. We demonstrate in-liquid IR $s$-SNOM vibrational nanoimaging and conformational identification of catalase nano-crystals and spatio-spectral analysis of biomimetic peptoid sheets with monolayer sensitivity and chemical specificity at the few zeptomole level. This work establishes the principles of in-liquid and in-situ IR $s$-SNOM spectroscopic chemical nano-imaging and its general applicability to biomolecular, cellular, catalytic, electrochemical, or other interfaces and nano-systems in liquids or solutions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Prediction of leaf chemistry by the use of visible and near infrared reflectance spectroscopy

The chemical content of dry, ground leaf material sampled from deciduous and conifer tree species from sites in Alaska, Wisconsin, and California was estimated using visible and shortwave IR spectroscopy. Seven chemical components - sugar, starch, protein, cellulose, total chlorophyll, lignin, and total nitrogen - were analyzed by wet chemical methods and their concentrations regressed against log 1/rho and first and second differences of log 1/rho (where rho is measured reflectance) at wavelengths selected by stepwise regression. Predictions of chemical concentrations based on cross validation suggest that this technique may be useful for extracting vegetation canopy biochemical information by remote sensing.

Card, Don H.↗

Canopy reflectance, photosynthesis, and transpiration. II - The role of biophysics in the linearity of their interdependence

The ability of satellite sensor systems to estimate area-averaged canopy photosynthetic and transpirative properties is evaluated. The near linear relationship between the simple ratio (SR) and normalized difference (ND) and the surface biophysical properties of canopy photosynthetically active radiation (PAR) absorption, photosynthesis, and bulk stomatal resistance is studied. The models utilized to illustrate the processes of canopy reflectance, photosynthesis, and resistance are described. The dependence of SR, the absorbed fraction of PAR, and canopy photosynthesis and resistance on total leaf area index is analyzed. It is noted that the SR and ND vegetation indices and vegetation-dependent qualities are near-linearly related due to the proportion of leaf scattering coefficient in visible and near IR wavelength regions. The data reveal that satellite sensor systems are useful for the estimation of photosynthesis and transpirative properties.

Sellers, P. J.↗

Numerical simulations of galactic wakes

We have performed a series of numerical simulations which examine the simple but realistic case of a galaxy with a smooth potential corresponding to a King profile, and with no interstellar medium. This corresponds to the case of an early-type cluster galaxy that has previously been stripped of its gas. The simulations provide a numerical basis for future work involving galaxies with interstellar media. We use a time-explicit finite difference code (Lufkin & Hawley 1992, ApJ submitted) to obtain solutions to the nonlinear equations for adiabatic flow in axisymmetry. The computational grid covers a region extending 500 kpc from a stationary galaxy radially and along the symmetry axis. We use a graded mesh, allowing for full resolution near the galaxy. Because the assumed potential has a finite depth, no artificial inner boundary condition is necessary; reflection symmetry at the axis is assumed. With a total grid size of 64 radial x 128 vertical, each run requires approximately 5 minutes of cpu time on the NCSA Cray-2.

Lufkin, Eric A.↗

Spectroscopic Investigation of Catalyst Inks and Thin Films Toward the Development of Ionomer Quality Control

As the production of polymer electrolyte fuel cells expands, novel quality control methods must be invented or adapted in order to support expected rates of production. Ensuring the quality of deposited catalyst layers is an essential step in the fuel cell manufacturing process, as the efficiency of a fuel cell is reliant on the catalyst layer being uniform at both the target platinum loading and the target ionomer content. Implementing a quality control method that is sensitive to these aspects is imperative, as wasting precious metals and other catalyst materials is expensive, and represents a potential barrier to entry into the field for manufacturers experimenting with novel deposition processes. In this work, we analyzed catalyst inks to determine if their ionomer content could be quantized spectroscopically. Attenuated total reflection (ATR) Fourier transform infrared spectroscopic technique was investigated producing a signal proportional to the ionomer content. ATR spectroscopy was able to quantitatively differentiate samples in which the ionomer to carbon mass ratio (I/C) varied between 0.9 and 3.0. The I/C ratio was correlated to the measured ATR signal near the CF 2 vibrational bands located between 1100 cm −1 and 1400 cm −1 . The experimental results obtained constitute a step toward the development of novel quality control methodologies for catalyst inks utilized by the fuel cell industry.

30 DIRECT ENERGY CONVERSION↗

Impact of divertor material on neutral recycling and discharge fueling in DIII-D

We report that experiments with the lower divertor of DIII-D during the Metal Rings Campaign (MRC) show that the fraction F of atomic D in the total recycling flux is material-dependent and varies through the ELM cycle, which may affect divertor fueling. Between ELMs, F C ~ 10% and FW ~ 40%, consistent with expectations if all atomic recycling is due to reflections. During ELMs, F C increases to 50% and F W to 60%. In contrast, the total D recycling coefficient including atoms and molecules R stays close to unity near the strike point where the surface is saturated with D. During ELMs, R can deviate from unity, increasing during high energy ELM-ion deposition (net D release) and decreasing at the end of the ELM which leads to ability of the target to trap the ELM-deposited D. The increase of R > 1 in response to an increase in ion impact energy Ei has been studied with small divertor target samples using Divertor Materials Evaluation System (DiMES). An electrostatic bias was applied to DiMES to change E i by 90 eV. On all studied materials including C, Mo, uncoated and W-coated TZM (>99% Mo, Ti, and Zr alloy), W, and W fuzz, an increase of E i transiently increased the D yield (and R) by ~10%. On C there was also an increase in the molecular D 2 yield, probably due to ion-induced D 2 desorption. Despite the measured increase in F on W compared to C, attached H-mode shots with OSP on W during MRC did not demonstrate a higher pedestal density. About 8% increase in the edge density could be seen only in attached L-mode scenarios. The difference can be explained by higher D trapping in the divertor and lower divertor fueling efficiency in H- versus L-mode.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Satellite-Sensor Calibration Verification Using the Cloud-Shadow Method

An atmospheric-correction method which uses cloud-shaded pixels together with pixels in a neighboring region of similar optical properties is described. This cloud-shadow method uses the difference between the total radiance values observed at the sensor for these two regions, thus removing the nearly identical atmospheric radiance contributions to the two signals (e.g. path radiance and Fresnel-reflected skylight). What remains is largely due to solar photons backscattered from beneath the sea to dominate the residual signal. Normalization by the direct solar irradiance reaching the sea surface and correction for some second-order effects provides the remote-sensing reflectance of the ocean at the location of the neighbor region, providing a known 'ground target' spectrum for use in testing the calibration of the sensor. A similar approach may be useful for land targets if horizontal homogeneity of scene reflectance exists about the shadow. Monte Carlo calculations have been used to correct for adjacency effects and to estimate the differences in the skylight reaching the shadowed and neighbor pixels.

Reinersman, P.↗

Canopy Level Solar Induced Fluorescence for Vegetation in Controlled Experiments

Solar induced chlorophyll fluorescence (SIF) was retrieved from high resolution reflectance spectra acquired one meter above saplings of three deciduous tree species during springtime (three weeks after leaf flush) and in late summer when foliage was mature. SIF was determined by application of the Fraunhofer Line Depth (FLD) Principal to above-canopy spectra acquired with an Analytical Spectral Devices (ASD) Fieldspec spectroradiometer (3.2 nm resolution with 1.2 nm sampling interval). SIF retrievals were made at the two atmospheric oxygen (O2) absorption features that occur in the chlorophyll fluorescence (ChlF) region (660 -780 nm). These telluric features are 02V, the broader and deeper feature centered at 760 nm, but located on the shoulder of the far-red ChlF peak at 740 nm; and 023, a narrow feature centered at 688 nm that is positioned near the red ChlF peak at 685 nm. Supporting, coincident leaf level fluorescence, reflectance, photochemical and other measurements were also made. At the leaf level, these measurements included in situ photosynthetic capacity (Pmax) and light adapted total chlorophyll fluorescence (Fs') collected at steady state under high light and controlled chamber conditions (e.g., temperature, PAR, humidity, and COz); optical properties (reflectance, transmittance, absorptance); chlorophyll and carotenoid content; specific leaf mass; carbon (C) and nitrogen (N) content; fluorescence emission spectra at multiple excitation wavelengths; the ChlF contribution to red (R) and far-red (FR) reflectance; fluorescence imagery; and fluorescence excitation-emission matrices (EEMs). The tree species examined were tulip poplar (Liriodendron tulipifera L.), red maple (Acer rubrum L.), and sweetgum (Liquidambar styraczflua L.), and each had been provided four levels of N augmentation (0, 19, 37, and 75 kg Nhectare seasonally) to simulate atmospheric deposition from air pollution. Whole-plant SIF measurements of these species were compared with SIF estimates derived using FluorMOD, a radiative transfer model that includes fluorescence properties of foliage, when provided with our supporting measurements. Simulated values for SIF were also compared with similar estimates made over three years for corn (Zea mays L) crops under N treatments (20, 50,70, and 140 kg Nhectare) and with corn and pepper (Capsicum annuum L.) plants provided dimethyl urea (DCMU, 0 and 5 x 10" M) which were grown in pots and grouped in artificial canopies for spectral measurements. For near-surface measurements of healthy and stressed vegetation, red SIF retrieved at 688 nm (023) varied between 2-7 mW/m(exp 2)/nm/sr while far-red SIF retrieved at 760 nm (O2A) varied between 0.5 and 4.0 mW/m(exp 2)/nm/sr. Typical values for the SIF red/far-red ratio ranged between 1.75 and 4.0. Relationships of SIF to spectral reflectance indices and foliar photochemical indices were examined, such as photosynthetic light use efficiency. Initial investigations of the variability in these measurements at the same leaf temperature for sunlit and shaded foliage showed us that shaded foliage produced higher ChlF and light use efficiency. Other factors that affect SIF determinations are discussed. These results will assist in determine the expected intensity of the SIF signal from vegetation near the surface, as well as to identify enhancements needed for FluorMOD (or other such models), and will assist in determining relationships of SIF to reflectance indices and carbon dynamics.

Middleton, E. M.↗

Structure of Complex Liquid–Liquid Extraction Organic Phases for Rare Earth Separations

Complex, multicomponent liquids with hierarchical structure and phase transitions are encountered in many natural and industrial processes, including in chemical separations. One notable example is aggregation and organic phase splitting in liquid–liquid extraction (LLE) of metal ions. While these two phenomena that have long been closely associated, a mechanistic link between mesoscale structure and the capacity-limiting organic phase splitting remains elusive due to complexity of these systems. Here, in this study, we combine small-angle X-ray scattering (SAXS), X-ray photon correlation spectroscopy (XPCS), and molecular dynamics simulation to reveal a comprehensive picture of structure at the nano- and mesoscale in these complex solutions. For the representative case of rare earth extraction from an acidic aqueous phase by a malonamide extractant in dodecane, we investigate a wide range of process-relevant extractant and acid concentrations to provide a complete picture of how aggregation depends on composition. We decompose organic phase structure from SAXS into two contributions, which together can capture the scattering at all compositions: composition fluctuations described by the Ornstein–Zernike equation at low wavenumber Q, and nanostructure modeled by a “pre-peak” at intermediate Q. The former contains information about the thermodynamics of demixing, while the latter reflects nanoscopic self-assembly of the extractant and extracted solutes. While fluctuations have typically not been considered in the literature, we find they in fact dominate the total structure for nearly all practical conditions. As only the fluctuations have a strong temperature response, we confirm this attribution with temperature-dependent SAXS measurements, including for extracted europium nitrate complexes. SAXS and XPCS measurements near the critical point find static and dynamic scaling consistent with theory. Overall, this new paradigm for understanding LLE organic phases connects composition, nanoscale, and mesoscale structuring to phase behavior, providing both a comprehensive picture of solution structure and a quantitative link between aggregation and third phase formation.

Peroutka, Allison A. [Argonne National Laboratory ↗

Formation of chondrules and CAIs by nebular processes

Chondrules are essential components of most chondritic meteorites. Carbonaceous chondrites, with the exception of CI chondrites, contain 30-50% chondrules, ordinary and enstatite chondrites even more. A better understanding of chondrule formation will therefore lead to an improved understanding of the origin of meteorites. Most studies of chondrules are, however, concerned with their texture and mineralogy. As chondrules, by definition, passed through a molten stage, their present texture and mineralogy can only provide information on conditions of crystallization from a melt and the subsequent solid-state cooling history. Information concerning chondrule formation is contained in their chemical and isotopic composition. The two most important observations relevant to the chemistry of the chondrules are their generally low Fe content and the large compositional variability of chondrules from a single meteorite, reflected in major variations of Mg/Si ratios, of Al and other refractory element abundances, total Fe, metal (Fe, Ni), and sulfide. This large compositional variability is surprising considering the uniform and nearly solar composition of bulk chondrites, which, in some cases, consist of more than 90% of chondrules.

Palme, H.↗

Global Distribution and 14-Year Changes in Erythemal Irradiance, UV Atmospheric Transmission, and Total Column Ozone 2005 – 2018 Estimated from OMI and EPIC Observations

Satellite data from the Ozone Measuring Instrument (OMI) and Earth Polychromatic Imaging Camera (EPIC) are used to study changes and global distribution of UV erythemal irradiance in mW/m(exp 2) E(ζ,φ,z,t) and the dimensionless UV index (E/25 mWm(exp 2)) over the Earth’s surface as a function of latitude ζ, longitude φ, altitude z, and time t. OMI time series data starting in January 2005 to December 2018 are used to estimate 14-year changes in erythemal irradiance, total column ozone TCO3, scene reflectivity LER, and aerosol absorption τA at specific land sites in the Northern and Southern Hemispheres using publicly available OMI data. Estimates of changes in atmospheric transmission ΔCτ(ζ,φ,z,t) derived from OMI measured cloud and haze reflectivity show an increase between 60°S to 45°S almost no average 14-year change from 55°S to 30°N but show an increase from 35°N to 55°N. This implies increased solar insolation at higher latitudes that suggests positive feedback for global warming. Changes in aerosol absorption of UV irradiance ΔCA(ζ,φ,z,t) derived from changes in τA are mostly in the equatorial region and at higher southern latitudes resulting in correlated changes in E. TCO3 derived from OMI data has increased at a rate of 2% per decade for the latitudes between 60°S to 10°N changing to a decrease of 1% per decade between 40°N to 60°N. The result is an average decrease in E(ζ,φ,z,t) at a rate of 2% per decade in the Southern Hemisphere and an increase between 40°N to 60°N. For some specific sites (latitudes from 55°S to 45°N) there has been little or no change in E(ζ,φ,z,t) for the period 2005 – 2018. Nearly half the sites show strong correlation effects of both short- and long-term cloud and absorbing aerosol change as well as anticorrelation with total column ozone change ΔTCO3. Synoptic EPIC data from the sunlit Earth are used to derive ozone and reflectivity needed for global images of the distribution of E(ζ,φ,z,t) from sunrise to sunset centered on the Americas, Europe-Africa, and Asia. EPIC data are used to show the latitudinal distribution of E(ζ,φ,z,t) from the equator to 75° for specific longitudes. Dangerously high amounts of erythemal irradiance (12 < UV index < 18) are found for many low latitude and high-altitude sites (e.g., San Pedro, Chile (2.45 km), La Paz, Bolivia (3.78 km). Lower UV indices at some equatorial or high-altitude sites (e.g., Quito, Ecuador) are moderated by the presence of persistent cloud effects. High UVI levels (UVI > 6) are also found at most mid-latitude sites during the summer months.

Ozone Measuring Instrument (OMI) and Earth Polychr↗