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Anhydrous vs Hydrated f-Element Acetate Polymers Dictated by the Stoichiometry of Protic Acidic/Basic Azole Mixtures

Continuing our investigations of ionic liquid (IL) based routes to a library of f-element/soft donor complexes which could be studied crystallographically, we have explored the dissolution of f-element salts in protic imidazole-based ILs containing only soft donors at high temperatures to drive off volatiles, including water and carboxylic or mineral acids. Here we present our results, reacting acidic and basic azoles in 1:3 or 1:1 stoichiometric compositions at elevated temperature, followed by saturation with Nd(OAc) 3 ·xH 2 O or Ce(OAc) 3 ·xH 2 O, which led to 13 new metal–acetate polymeric complexes identified by single-crystal X-ray diffraction. We found that the diversity in coordination modes of the simple acetate ligand that interfere with substitution of the softer N donors led to several readily crystallizable complexes forming two distinct groups with respect to f-element interaction with the ionic liquid precursors. When the acidic/basic azole ratio was 1:3, acetate and a neutral basic azole were found to be coordinated to the metal centers but no water, although in one case (2) water was observed in the secondary coordination sphere: [Ce(μ 2 -OAc) 3 (C 1 im)] n (1, C 1 im = 1-methylimidazole), [Nd(μ 2 -(OAc) 3 (C 1 im)] n ·nH 2 O (2), [Ce(μ 2 -OAc) 3 (C 2 im)] n (3, C 2 im = 1-ethylimidazole), [Ln(μ 2 -OAc) 3 DMF] n (Ln = Nd (4), Ce (5); dimethylformamide (DMF) was substituted for the azole mixture), and [Nd(μ 2 -OAc) 3 (C 4 im)] n (6, C 4 im = 1-butylimidazole). However, when the stoichiometric ratio was 1:1, water was always observed coordinated to the metal ions with the acidic azole included in the structure as a solvate or cocrystal, despite a higher reaction temperature: [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(1,2,3-Taz) (7, 1,2,3-Taz = 1,2,3-triazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(4,5-DCim) (Ln = Nd (8), Ce (9), 4,5-DCim = 4,5-dicyanoimidazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(3,5-diNH 2 -1,2,4-Taz) (Ln = Nd (10), Ce (11), 3,5-diNH 2 -1,2,4-Taz = 3,5-diamino-1,2,4-triazole), [Ce(μ 2 -OAc) 3 (OH 2 )] n ·n(3-NH 2 -1,2,4-Taz) (12, 3-NH 2 -1,2,4-Taz = 3-amino-1,2,4-triazole), and [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(5-NH 2 -Tz) (13, 5-NH2-Tz = 5-aminotetrazole). All of the compounds retain the Ln:OAc– ratio of 1:3 and form 1D polymeric chains; however, they exhibit a variety of coordination modes affecting the degree of chain condensation. The isolation of both hydrated and anhydrous products revealed different abilities of the investigated soft N-donors to compete with O-donors finding their place in the coordination sphere of the lanthanide or in the crystal lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing Impacts of Plant Stoichiometric Traits on Terrestrial Ecosystem Carbon Accumulation Using the E3SM Land Model

Carbon (C) enters into the terrestrial ecosystems via photosynthesis and cycles through the system together with other essential nutrients (i.e., nitrogen [N] and phosphorus [P]). Such a strong coupling of C, N, and P leads to the theoretical prediction that limited nutrient availability will limit photosynthesis rate, plant growth, and future terrestrial C dynamics. However, the lack of reliable information about plant tissue stoichiometric constraints remains a challenge for quantifying nutrient limitations on projected global C cycling. In this study, we harmonized observed plant tissue C:N:P stoichiometry from more than 6,000 plant species with the commonly used plant functional type framework in global land models. Using observed C:N:P stoichiometry and the flexibility of these ratios as emergent plant traits, we show that observationally constrained fixed plant stoichiometry does not improve model estimates of present-day C dynamics compared with unconstrained stoichiometry. However, adopting stoichiometric flexibility significantly improves model predictions of C fluxes and stocks. The 21st century simulations with RCP8.5 CO 2 concentrations show that stoichiometric flexibility, rather than baseline stoichiometric ratios, is the dominant controller of plant productivity and ecosystem C accumulation in modeled responses to CO 2 fertilization. The enhanced nutrient limitations and plant P use efficiency mainly explain this result. This study is consistent with the previous consensus that nutrient availability will limit xfuture land carbon sequestration but challenges the idea that imbalances between C and nutrient supplies and fixed stoichiometry limit future land C sinks. We show here that it is necessary to represent nutrient stoichiometric flexibility in models to accurately project future terrestrial ecosystem carbon sequestration.

54 ENVIRONMENTAL SCIENCES↗

Mechanism and kinetics of the oxidation of 1,3-butadien-1-yl (n-C 4 H 5 ): a theoretical study

Here, ab initio CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) calculations of the C 4 H 5 O 2 potential energy surface have been combined with Rice–Ramsperger–Kassel–Marcus Master Equation (RRKM-ME) calculations of temperature- and pressure-dependent rate constants and product branching ratios to unravel the mechanism and kinetics of the n-C 4 H 5 + O 2 reaction. The results indicate that the reaction is fast, with the total rate constant being in the range of 3.4–5.6 × 10 –11 cm 3 molecule –1 s –1 . The main products include 1-oxo-n-butadienyl + O and acrolein + HCO, with their cumulative yield exceeding 90% at temperatures above 1500 K. Two conformers of 1-oxo-n-butadienyl + O are formed via a simple mechanism of O 2 addition to the radical site of n-C 4 H 5 followed by the cleavage of the O–O bond proceeding via a van der Waals C 4 H 5 O∙∙∙O complex. Alternatively, the pathways leading to acrolein + HCO involve significant reorganization of the heavy-atom skeleton either via formal migration of one O atom to the opposite end of the molecule or its insertion into the C1–C2 bond. Not counting thermal stabilization of the initial peroxy adducts, which prevails at low temperatures and high pressures, all other products share a minor yield of under 5%. Rate constants for the significant reaction channels have been fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the oxidation of aromatic molecules and 1,3-butadiene. As a secondary reaction, n-C 4 H 5 + O 2 can be a source for the formation of acrolein observed experimentally in oxidation of the phenyl radical at low combustion temperatures, whereas another significant (secondary) product of the C 6 H 5 + O 2 reaction, furan, could be formed through unimolecular decomposition of 1-oxo-n-butadienyl. Both the n-C 4 H 5 + O 2 reaction and unimolecular decomposition of its 1-oxo-n-butadienyl primary product are shown not to be a substantial source of ketene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetism and its coexistence with superconductivity in CaK(Fe 0.949 Ni 0.051 ) 4 As 4 : Muon spin rotation/relaxation studies

Here, the magnetic response of Ca K ( Fe 0.949 Ni 0.051 ) 4 As 4 was investigated by means of the muon spin rotation/relaxation. The long-range commensurate magnetic order sets in below the Néel temperature T N = 50.0 ( 5 ) K. The density-functional theory calculations have identified three possible muon stopping sites. The experimental data were found to be consistent with only one type of magnetic structure, namely, the long-range magnetic spin-vortex-crystal order with the hedgehog motif within the a b plane and the antiferromagnetic stacking along the c direction. The value of the ordered magnetic moment at T ≈ 3 K was estimated to be m Fe = 0.38 ( 11 ) μ B ( μ B is the Bohr magneton). A microscopic coexistence of magnetic and superconducting phases accompanied by a reduction of the magnetic order parameter below the superconducting transition temperature T c ≃ 9 K is observed. Comparison with 11, 122, and 1144 families of Fe-based pnictides points to existence of correlation between the reduction of the magnetic order parameter at T → 0 and the ratio of the transition temperatures T c / T N . Such correlations were found to be described by Machida's model for coexistence of itinerant spin-density-wave magnetism and superconductivity [K. Machida, J. Phys. Soc. Jpn. 50 , 2195 (1981) ; S. L. Bud'ko et al. , Phys. Rev. B 98 , 144520 (2018) ].

36 MATERIALS SCIENCE↗

Ion Acceleration in Solar Flares

Solar flares are among the most energetic and interesting phenomena in the Solar system, releasing up to 1032 ergs of energy on timescales of several tens of seconds to several tens of minutes. Much of this energy is in the form of suprathermal electrons and ions, which remain trapped at the Sun and produce a wide variety of radiations, as well as escape into interplanetary space, where they can be directly observed. The radiation from trapped particles consists in general of (1) continuum emission; (2) narrow gamma-ray nuclear deexcitation lines; and (3) high-energy neutrons observed in space or by ground-based neutron monitors. The particles that escape into space consist of both electrons and ions, which often have compositions quite different than that of the ambient solar atmosphere. Flares thus present many diagnostics of the particle acceleration mechanism(s), the identification of which is the ultimate goal of flare research. Moreover, flares in fact offer the only opportunity in astrophysics to study the simultaneous energization of both electrons and ions. Hopefully, an understanding of flares with their wealth of diagnostic data will lead to a better understanding of particle acceleration at other sites in the Universe. It is now generally accepted that flares are roughly divided into two classes: impulsive and gradual. Gradual events are large, occur high in the corona, have long-duration soft and hard X-rays and gamma rays, are electron poor, are associated with Type II radio emission and coronal mass ejections (CMEs), and produce energetic ions with coronal abundance ratios. Impulsive events are more compact, occur lower in the corona, produce short-duration radiation, and exhibit dramatic abundance enhancements in the energetic ions. Their He-3/He-4 ratio is - 1, which is a huge increase over the coronal value of about 5 x 10(exp -4), and they also posses smaller but still significant enhancements of Ne, Mg, Si, and Fe relative to He-4, C, N, and O. Specifically, above about 1 MeV nucleon(exp -1), the ratio of Fe to O is about 8 times larger than in the corona or in gradual flares, while the ratio of Ne, Mg, and Si to O is about 3 times higher; He-4, C, N, and 0 are not enchanced with respect to each other. In addition to these elemental enhancements, Ne and Mg have isotopic enhancements as well. The general scenario that has emerged from these (and other) observations is that energetic particles in gradual events are accelerated by a CME-driven shock, while those particles in impulsive events are accelerated by another mechanism(s).

Miller, James A.↗

Isotopic constraints on the origin of meteoritic organic matter

Salient features of the isotopic distribution of H, C and N in the organic material found in carbonaceous meteorites are noted. Most organic fractions are strongly enriched in D with respect to the D/H ratio characteristic of H2 in the protosolar system; substantial variations in C-13/C-12 ratio are found among different molecular species, with oxidised species tending to be C-13 enriched relative to reduced species; some homologous series reveal systematic decrease in C-13/C-12 with increasing C number; considerable variation in N-15/N-14 ratio is observed within organic matter, though no systematic pattern to its distribution has yet emerged; no interelement correlations have been observed between isotope enrichments for the different biogenic elements. The isotopic complexity echoes the molecular diversity observed in meteoritic organic matter and suggests that the organic matter was formed by multiple processes and/or from multiple sources. However, existence of a few systematic patterns points towards survival of isotopic signatures characteristic of one or more specific processes. The widespread D enrichment implies either survival of many species of interstellar molecule or synthesis from a reservoir containing a significant interstellar component. Several of the questions raised above can be addressed by more detailed determination of the distribution of the H, C and N isotopes among different well-characterized molecular fractions. Thus, the present study is aimed at discovering whether the different amino acids have comparable D enrichments, which would imply local synthesis from a D-enriched reservoir, or very viable D enrichments, which would imply survival of some interstellar amino acids. The same approach is also being applied to polycyclic aromatic hydrocarbons. Because the analytical technique employed (secondary ion mass spectrometry) can acquire data for all three isotopic systems from each molecular fraction, any presently obscured interelement isotopic correlation should also be revealed, which will aid in identifying pertinent synthetic processes.

Kerridge, J. F.↗

Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.

impedance↗

Isotopic microanalysis of returned comet nucleus samples

If isotopic measurements of interplanetary dust particles (IDPs) and primitive meteorites can serve as a guide to the isotopic analysis of returned comet nucleus material, an essential requirement will be the capability for microanalysis. The reason is that in both types of extraterrestrial samples large isotopic heterogeneities on a small spatial scale have become apparent once it was possible to measure isotopes in small samples. In the discovery of large isotopic anomalies the ion microprobe has played a significant role because of its high spatial resolution for isotopic ratio measurements. The largest isotopic anomalies in C, N, O, Mg, Si, Ca and Ti found to date were measured by ion microprobe mass spectrometry. The most striking examples are D/H measurements in IDPs and isotopic measurements of C, N and Si in SiC from the CM chondrites Murray and Murchison.

Zinner, Ernst↗

FUN-BioCROP model with litter decomposition parameters derived from the LIDET dataset

This repository contains the code and data necessary to run the FUN-BioCROP (Fixation and Uptake of Nitrogen-Bioenergy Carbon, Rhizosphere, Organisms, and Protection) model with litter decomposition parameters derived from a modified Monte Carlo simulation that used the Long-term Intersite Decomposition Experiment Team dataset. Related publication:Juice, S.M., Ridgeway, J.R., Hartman, M.D., Parton, W.J., Berardi, D.M., Sulman, B.N., Allen, K.E., & Brzostek, E.R. Reparameterizing litter decomposition using a simplified Monte Carlo method improves litter decay simulated by a microbial model and alters bioenergy soil carbon estimates. Description of Files: FUNBioCROP_LIDET Study.Rmd R code with FUN-BioCROP model that can be run with 10 different sets of parameters for litter decomposition (Baseline, LIDET, or eight other best parameter sets identified in the modified Monte Carlo simulation. CORPSE Functions_Bioenergy_V2.R Code with CORPSE model functions, called by FUNBioCROP_LIDET Study.Rmd Model Input Data: bulk.csv, bulk_till.csv, rhizo.csv, rhizo_till.csv, litter.csv Initial C and N (kg C or N/m2) pool values for each soil compartment, final values from spin up. All five files have the same columns: (Column - Description - Units) uFastC - Unprotected fast decomposing carbon - kg carbon/m2 uSlowC - Unprotected slow decomposing carbon - kg carbon/m2 uNecroC - Unprotected necromass carbon - kg carbon/m2 pFastC - Protected fast decomposing carbon - kg carbon/m2 pSlowC - Protected slow decomposing carbon - kg carbon/m2 pNecroC - Protected necromass carbon - kg carbon/m2 livingMicrobeC - Carbon in living microbial biomass - kg carbon/m2 uFastN - Unprotected fast decomposing nitrogen - kg nitrogen/m2 uSlowN - Unprotected slow decomposing nitrogen - kg nitrogen/m2 uNecroN - Unprotected necromass nitrogen - kg nitrogen/m2 pFastN - Protected fast decomposing nitrogen - kg nitrogen/m2 pSlowN - Protected slow decomposing nitrogen - kg nitrogen/m2 pNecroN - Protected necromass nitrogen - kg nitrogen/m2 inorganicN - Inorganic nitrogen - kg nitrogen/m2 CO2 - Carbon in carbon dioxide - kg carbon/m2 livingMicrobeN - Nitrogen in living microbial biomass - kg nitrogen/m2 Model Input Data: FluxTower_AvgSoilT.csv: Average daily soil temperature (oC) at 10 cm depth at University of Illinois Urbana-Champaign (UIUC) Energy Farm flux tower from 7/2008-3/2016. (One year of averaged data) Model Input Data: FluxTower_AvgSoilVWC.csv: Average daily soil volumetric water content (VWC) at 10 cm depth at UIUC Energy Farm flux tower from 7/2008-3/2016. (One year of averaged data) Model Input Data: input_CCS_LIDET Study.csv: This file has daily data to run FUN-BioCROP (Column - Description - Units): yr - calendar year - year doy - day of year (1 to 365) (no leap year) - day anpp - aboveground NPP (DayCent) - kg C/m2/day bnpp - belowground NPP (DayCent) - kg C/m2/day aglivc - live aboveground biomass carbon (DayCent) - kg C/m2 bglivcj - live juvenile fine root biomass carbon (DayCent) - kg C/m2 bglivcm - live mature fine root biomass carbon (DayCent) - kg C/m2 aglivn - live aboveground biomass nitrogen (DayCent) - kg N/m2 bglivnj - live juvenile fine root biomass nitrogen (DayCent) - kg N/m2 bglivnm - live mature fine root biomass nitrogen (DayCent) - kg N/m2 nyr - simulation year - year cult - indicates a cultivation event (0 or 1) crop - indicates a new crop (0 or 1) fert - indicates a fertilizer event (0 or 1) frst - indicates the first day of the growing season (0 or 1) harv - indicates a harvest event (0 or 1) last - indicates the end of the growing season (0 or 1) croptype - crop type (0=none; 1=alfalfa; 2=corn; 3=grass clover pasture; 4=soybean; 5=wheat) cropsrl - crop specific root length - mm/g root cultrhizmix - fraction of rhizosphere mixed with bulk soil during cultivation (0.0-1.0) - fraction cultlitmix - fraction of litter mixed with bulk soil during cultivation (0.0-1.0) - fraction harvremov - fraction of above ground biomass removed during harvest (0.0-1.0) - fraction fertamt - fertilization amount - g N/m2 lifehist - plant life history (0 = annual, 1 = perennial) froot_turnover_c - amount of C in fine root turnover - kg C/m2 froot_turnover_n - amount of N in fine root turnover - kg N/m2 agrd_turnover_c - amount of C in aboveground biomass turnover - kg C/m2 agrd_turnover_n - amount of N in aboveground biomass turnover - kg N/m2 leaf_litter_fastfrac - Fast decomposing fraction of leaf litter (0.0-1.0) - fraction root_litter_fastfrac - Fast decomposing fraction of root litter (0.0-1.0) - fraction root_diameter - root diameter - mm root_length - root length - mm root/m2 rhizo_frac - fraction of total soil volume that is rhizosphere (0.0 - 1.0) - fraction date - date in format YYYY-MM-DD Instructions: Save the model code ("FUN-BioCROP_LIDET Study.Rmd") and accompanything files (data streams and CORPSE function code) in the same folder. In model code "Chunk 3: Load CORPSE Data Streams" set the working directory (setwd) to the folder with the files saved in step #1. In "Chunk 5: Define LIDET parameter sets" select the litter decomposition parameter set to be used in the run, and comment out all other sets. If changing any parameter values, edit them in "Chunk 6: Load parameters." Run all chunks up to and including "Chunk 10: Prepare Data for Export." In "Chunk 11: Export Output Data" edit data frames for export and filenames, as necessary. "Chunk 12: Graph Total Soil C" makes a figure of C remaining over the model run period. Description of each model chunk (in file FUN-BioCROP_LIDET Study.Rmd): Chunk 1: Remove all functions, clear memory. Removes all functions from R environment, clears the memory. Chunk 2: Load Packages. Loads packages necessary to run the code. Chunk 3: Load CORPSE Data Streams. Sets the working directory and loads the data files necessary to run CORPSE. Chunk 4: Load CORPSE Functions. Loads the R script with CORPSE functions from the working directory, "CORPSE Functions_Bioenergy_V2.R". Chunk 5: Define LIDET parameter sets. Has ten different parameter sets for litter decomposition tested in this study: Baseline parameters, LIDET parameters, and the other 8 best performing parameter sets identified in the modified Monte Carlo. To run the model, all but one parameter set must be commented out. Chunk 6: Load Parameters. Loads all fixed parameters to run the model. Data frame with definitions of parameters is in the CORPSE function script "CORPSE Functions_Bioenergy_V2.R" Chunk 7: Prepare Data Streams. Takes data streams loaded in Chunk 3 and puts them in the format necessary to run the model. The model is coded to run at least two sites at a time, so if only one site is being run it must be run in duplicate. Individual data tables of daily values are created in this chunk from the input data file. Chunk 8: Set Initial Conditions. Creates data tables of soil C and N pools for each soil compartment (rhizo_till, rhizo, bulk_till, bulk, litter) and loads initial values into the data tables. Creates lists for each soil compartment to hold model output. Chunk 9: Load FUN Data and Set Up Matrices. Uses DayCent data to calculate FUN input data: root and leaf N demand, total N demand, plant CN, leaf N available for retranslocation, and litter production. Creates matrices for FUN model outputs. Chunk 10: Run Model. Runs the model. Chunk 11: Prepare Data for Export. Combines data from each day saved as lists into data frames for each soil compartment. Adds values from all soil compartments together to calculate total soil values, creates separate data frames for each soil C and N pool (e.g., protected slow C) for the total soil value. Adds different C and N pools together to calculate total soil C and N for all layers. Creates data frame of ratio of protected to unprotected SOC. Organizes FUN data for export. Chunk 12: Export Results. Exports CSV files of model results to the working directory. Chunk 13: Graph Total Soil C. Makes figure of C remaining over time. Related Links: Original FUN-BioCROP model: https://github.com/BrzostekEcologyLab/FUN-BioCROP LIDET dataset: https://andlter.forestry.oregonstate.edu/data/abstract.aspx?dbcode=TD023

Juice, Stephanie↗

Properties of the solar wind electrons between 1 and 3.3 AU from Ulysses thermal noise measurements

In order to describe the distribution function f(v) of the solar wind electrons, the simplest model which is commonly used consists of the sum of two Maxwellians representing two distinct populations: a core (density n(sub c), temperature T(sub c)) and a halo (density n(sub h), temperature T(sub h)). It is possible, with the latter assumptions on the electron f(v), to determine the quasi-thermal noise (QTN) induced on an antenna by the motion of the ambient electrons in the solar wind. Using this distribution and the spectroscopy of thermal noise measurements from the radio receiver on Ulysses in the ecliptic plane, we deduce the total electron density N(sub e), the core temperature T(sub c), and the core and halo kinetic pressures N(sub c)T(sub c) and N(sub h)T(sub h). From these electron parameters, we can define a 'global' electron temperature as T(sub e) = (N(sub c)T(sub c) + N(sub h)T(sub h))/N(sub e). Here we present different radial gradients of T(sub e), between 1 and 3.3 AU, as a function of three classes of N(sub e) at 1 AU: low, intermediate, and high densities. In general all these gradients are found to be positive with different polytrope power law indexes between N(sub e) and T(sub e), which are in general lower than unity. We also show different behaviors of the ratio N(sub h)T(sub h)/N(sub c)T(sub c) for each density class considered. Some possible interpretations for these observations are discussed.

Maksimovic, M.↗

On the 2018 Outburst of the Accreting Millisecond X-Ray Pulsar Swift J1756.9-2508 As Seen with NICER

We report on the coherent timing analysis of the 182 Hz accreting millisecond X-ray pulsar SwiftJ1756.92508during its 2018 outburst as observed with the Neutron Star Interior Composition Explorer (NICER). Combiningour NICER observations with Rossi X-ray Timing Explorer observations of the 2007 and 2009 outbursts, we alsostudied the long-term spin and orbital evolution of this source. We find that the binary system is well describedby a constant orbital period model, with an upper limit on the orbital period derivative of Pb < 7.4 ´ 10-13 ss1.Additionally, we improve upon the source coordinates through astrometric analysis of the pulse arrival times,finding R.A.=17h56m57 18±0 08 and decl.=25°0627 8±3 5, while simultaneously measuring thelong-term spin frequency derivative as n = -7.3 ´ 10-16 Hzs1. We briefly discuss the implications of thesemeasurements in the context of the wider population of accreting millisecond pulsars. We reported on the coherent timing analysis of the 2018 outburst of Swift J1756 as observed with NICER. Consistent with analyses of the previous outbursts (Krimm et al. 2007b; Patruno et al. 2010), we find that the X-ray pulsations have energy dependent amplitudes; the fractional amplitude of the fundamental increases with energy, whereas the fractional amplitude of the harmonic shows a slight decline with energy. This energy dependent behavior is not unusual in AMXPs (Patruno & Watts 2012) and can be interpreted in terms of the thermal emission from the stellar hotspot and reprocessing in the accretion column (e.g., Gierliński et al. 2002; Ibragimov & Poutanen 2009). The pulse arrival times of the 2018 outburst are well described by a timing model consisting of a circular orbit with a constant spin frequency. The pulse phases with respect to this model do not show spurious residuals with time or orbital phase, and no evidence is found that the pulse arrival times exhibit an additional delay associated with passing through the gravitational well of the companion star (Shapiro delay). We note, however, that the expected Shapiro delay is given as (Shapiro et al. 1971) Equation (5) where Φ is the orbital phase, G is the gravitational constant, c is the speed of light, and i is the inclination. Even for the maximum allowed companion mass, ${M}_{C}=0.030\,{M}_{\odot }$ (Krimm et al. 2007b, but see Section 4.2 for more details) and an inclination of 90°, the largest delay we can expect is only 4 μs. As this time-delay is smaller than the uncertainty on our phase residuals by nearly two orders of magnitude (see Figure 1), we are not sensitive to Shapiro delays in Swift J1756. Comparing our measurements for the 2018 outburst with those of the 2007 and 2009 outbursts as observed with RXTE, we analyzed the long-term evolution of this source. We found that the binary system is consistent with having a constant orbital period and that the pulsar shows a spin frequency derivative of $\dot{\nu }=-7.3\times {10}^{-16}\,\mathrm{Hz}\,{{\rm{s}}}^{-1}$. 4.1. Spin-down Evolution The long-term spin frequency derivative measured in Swift J1756 is of the same order as the spin frequency derivatives measured in other AMXPs (Hartman et al. 2008; Patruno 2010; Riggio et al. 2011). This frequency change is most likely driven by the neutron star's loss of rotational energy. If so, then the spin-down luminosity is given as Equation (6) where I represents the neutron star moment of inertia. The long-term spin-down of a neutron star is usually assumed to be dominated by the braking torque associated with a spinning magnetic field. Assuming this mechanism is responsible for the observed spin-down in Swift J1756, we can compute the magnetic dipole moment as (Spitkovsky 2006) Equation (7) where α is the misalignment angle between the rotational and magnetic poles. Considering α = 0°–90°, we then find a magnetic field strength of $B\simeq (4\mbox{--}6)\times {10}^{8}$ G at the stellar magnetic poles. This magnetic field strength estimate is in line with those obtained for other accreting millisecond pulsars (see Mukherjee et al. 2015 and references therein). 4.2. Orbit Evolution The observed long-term binary evolution of Swift J1756 is consistent with this source having a constant orbital period and a lower limit on the evolutionary timescale of Equation (8) Binary evolution theory predicts that systems of this type evolve due to angular momentum loss through gravitational radiation (Kraft et al. 1962; Rappaport et al. 1982; Verbunt 1993). For conservative mass transfer, the binary period derivative is given by di Salvo et al. (2008), Equation (9) where MNS is the neutron star mass, $q={M}_{C}/{M}_{\mathrm{NS}}$ is the binary mass ratio, and −1/3 < n < 1 is the mass–radius index of the companion star. Depending on the source inclination, Krimm et al. (2007b) derived a companion mass of ${M}_{C}\,=0.007\mbox{--}0.022\,{M}_{\odot }$ for a neutron star mass of 1.4 ${M}_{\odot }$. For a neutron star mass of 2.2 ${M}_{\odot }$, the allowed range increased to ${M}_{C}=0.009\mbox{--}0.030\,{M}_{\odot }$. In both cases, they assumed an upper limit on the inclination of i < 85°, motivated by the fact that Swift J1756 does not show eclipses in its light curve. Accounting for the extreme cases of stellar masses and n, the binary may either be contracting or expanding. In either case, however, the rate of change is limited to $| {\dot{P}}_{b}| \lesssim 7\times {10}^{-14}$ s s−1, which is well below the upper limit obtained in this work. Although the binary evolution timescale we obtain for Swift J1756 is consistent with theory, it is worth noting that this is not generally true for low-mass X-ray binaries (see Patruno et al. 2017, for a comprehensive discussion). The AMXP SAX J1808.4–3658, in particular, has been found to evolve on a much shorter timescale, with a first derivative on the orbital period of $3.5\times {10}^{-12}$ s s−1 (Hartman et al. 2008; Patruno et al. 2012; Sanna et al. 2017a). Two models have been proposed to explain this discrepancy: highly nonconservative mass transfer due to irradiation of the companion star by the pulsar (di Salvo et al. 2008; Burderi et al. 2009), and spin–orbit coupling in the companion star (Hartman et al. 2008, 2009). While the latter depends on the companion star, and may vary from source to source, the former should operate in all AMXPs (see also Patruno 2017; Sanna et al. 2017c), including Swift J1756. The spin-down luminosity impinging on the companion star can be estimated as Equation (10) where ${\dot{E}}_{\mathrm{abl}}$ is the ablation luminosity, RL2 is the Roche lobe radius of the companion (Eggleton 1983), and a the binary separation. The irradiation fraction is $f={\dot{E}}_{\mathrm{abl}}/{\dot{E}}_{\mathrm{sd}}$, which, accounting for the range of allowed neutron star and companion masses, evaluates to f = 0.15%–0.35%. The associated mass loss for the companion is given by Equation (11) such that, assuming an efficiency of η = 100%, ${\dot{M}}_{C}\,\sim -3\times {10}^{-10}\,{M}_{\odot }$ yr−1. The effect of this mass loss on the orbital period follows through the relation (Frank et al. 2002) Equation (12) giving a period derivative due to mass loss of ${\dot{P}}_{b,\mathrm{ML}}\,=5\times {10}^{-12}$ s s−1. This value is well above our limit on the period derivative. Hence, in order for this mechanism to be consistent with our observations of Swift J1756, the efficiency at which the companion star converts the incident luminosity into mass loss must be η < 15%. This value is very different from the 40% required in SAX J1808.4–3658 (Patruno et al. 2016) and is instead in line with the <5% efficiency determined for IGR J00291+5934 (Patruno 2017). This work was supported by NASA through the NICER mission and the Astrophysics Explorers Program, and made use of data and software provided by the High Energy Astrophysics Science Archive Research Center (HEASARC). P.B. was supported by an NPP fellowship at NASA Goddard Space Flight Center. D.A. acknowledges support from the Royal Society.

Bult, Peter↗

Isotopic Measurements of Organic Sulfonates From The Murchison Meteorite

Organic sulfonates and phosphonates have been extracted from the Murchison meteorite for stable isotope measurements. Preliminary stable isotope measurements of individual alkyl sulfonates, R-SO3H (R=C(sub n)H(sub 2n+l)), are shown. These compounds were found in aqueous extracts of Murchison. Both groups show trends similar to other homologous series of organic compounds indigenous to Murchison. Molecular abundances decrease with increasing carbon number, and all possible isomers at each carbon number (through C-4) are present. Carbon isotope measurements of the sulfonates show a decrease in the C-13/C-12 ratio with increasing carbon number. The overall objectives of this project are to obtain dime element carbon, hydrogen, and sulfur - intramolecular isotopic analyses of individual sulfonates, and isotopic measurement of carbon and hydrogen of the phosphonates as a group. The Murchison meteorite is the best characterized carbonaceous chondrite with respect to organic chemistry. The finding of organic sulfonates and phosphonates in Murchison is of interest because they are the first well-characterized series of sulfur and phosphorus containing organic compounds found in meteorites. Also, meteorites, comets, and interplanetary dust particles may have been involved in chemical evolution on the early Earth. Because of the critical role of organic phosphorus and sulfur in all living systems, it is particularly interesting to see examples of abiotic syntheses of these classes of compounds. The study of the isotopic composition of the sulfonates and phosphonates can yield insight into their possible interstellar origin as well as their mechanisms of synthesis in the early solar system. Previous isotopic analyses of other classes of organic compounds indigenous to meteorites, e.g., amino acids, carboxylic acids, and hydrocarbons indicate the possibility that interstellar molecules were incorporated into meteorite parent bodies. In these compounds the ratios of heavy to light isotopes of hydrogen (D/H), carbon (C-13/C-12), and nitrogen (N-15/N-14), are anomalous relative to bulk terrestrial and meteoritic values. In some cases, the D/H ratios approach those observed for molecules in interstellar clouds.

Cooper, G. W.↗

Ice and Supercooled Liquid Water Distributions over the Southern Ocean based on In Situ Observations and Climate Model Simulations

Three climate models are evaluated using in situ airborne observations from the Southern Ocean Clouds, Radiation, Aerosol Transport Experimental Study (SOCRATES) campaign. The evaluation targets cloud phases, microphysical properties, thermodynamic conditions, and aerosol indirect effects from –40°C to 0°C. Compared with 580-s averaged observations (i.e., 100 km horizontal scale), the Community Atmosphere Model version 6 (CAM6) shows the most similar result for cloud phase frequency distribution and allows more liquid-containing clouds below –10°C compared with its predecessor—CAM5. The Energy Exascale Earth System Model (E3SM) underestimates (overestimates) ice phase frequencies below (above) –20°C. CAM6 and E3SM show liquid and ice water contents (i.e., LWC and IWC) similar to observations from –25°C to 0°C, but higher LWC and lower IWC than observations at lower temperatures. Simulated in-cloud RH shows higher minimum values than observations, possibly restricting ice growth during sedimentation. As number concentrations of aerosols larger than 500 nm (Na 500 ) increase, observations show increases of LWC, IWC, liquid, and ice number concentrations (N liq , N ice ). Number concentrations of aerosols larger than 100 nm (Na 100 ) only show positive correlations with LWC and N liq . From –20°C to 0°C, higher aerosol number concentrations are correlated with lower glaciation ratio and higher cloud fraction. From –40°C to –20°C, large aerosols show positive correlations with glaciation ratio. CAM6 shows small increases of LWC and N liq with Na 500 and Na 100 . E3SM shows small increases of N ice with Na 500 . Altogether, CAM6 and E3SM underestimate aerosol indirect effects on ice crystals and supercooled liquid droplets over the Southern Ocean.

54 ENVIRONMENTAL SCIENCES↗

Multiphase gas in quasar absorption-line systems

In the standard model for H I Lyman-limit (LL) quasar absorption-line systems, the absorbing matter is galactic disk and halo gas, heated and photoionized by the metagalactic radiation field produced by active galaxies. In recent Hubble Space Telescope (HST) observations (Reimers et al. 1992; Vogel & Reimers 1993; Reimers & Vogel 1993) of LL systems along the line of sight to the quasar HS 1700+6416, surprisingly high He I/H I ratios and a wide distribution of column densities of C, N, and O ions are deduced from extreme ultraviolet absorption lines. We show that these observations are incompatible with photoionization equilibrium by a single metagalactic ionizing background. We argue that these quasar absorption systems possess a multiphase interstellar medium similar to that of our Galaxy, in which extended hot, collisionally ionized gas is responsible for some or all of the high ionization stages of heavy elements. From the He/H ratios we obtain -4.0 less than or = log U less than or = -3.0, while the CNO ions are consistent with hot gas in collisional ionization equilibrium at log T = 5.3 and (O/H) = -1.6. The supernova rate necessary to produce these heavy elements and maintain the hot-gas energy budget of approximately 10(exp 41.5) ergs/s is approximately 10(exp -2)/yr, similar to that which maintains the 'three-phase' interstellar medium in our own Galaxy. As a consequence of the change in interpretation from photoionized gas to a multiphase medium, the derived heavy-element abundances (e.g., O/C) of these systems are open to question owing to substantial ionization corrections for unseen C V in the hot phase. The metal-line ratios may also lead to erroneous diagnostics of the shape of the metagalactic ionizaing spectrum and the ionizing parameter of the absorbers.

Giroux, Mark L.↗

Surveying Phase Modifier Functional Groups for Applications to Ln(III) Separations

The application of N,N,N',N'-tetraoctyl diglycolamide (TODGA) in solvent extraction systems for lanthanide (Ln) separations is well understood. In these systems, the formation of a third phase has motivated the use of phase modifiers to enable higher concentrations of H + and Ln common to industrial processes. Several different phase modifiers with applications to diglycolamide (DGA) systems have previously been reported, with a focus on tri-n-butyl phosphate (TBP), N,N'-dihexylactanamide (DHOA), N,N-dioctyl-2-hydroxyacetamide (DOHyA), N,N'-dimethyl-N,N'-dioctylhexylethoxy malonamide (DMDOHEMA), and octanol. While the primary utility of phase modifiers is the increased metal loading, they can have significant effects on the metal distribution ratios, which are well described by the energetics of the extraction process itself. However, the mechanisms by which phase modifiers impact distribution ratios are not generally understood. This work considers the ability of phase modifiers to affect Ln distribution ratios by using phase modifiers with two different functional groups (–Cl and –C≡N) and an octyl alkyl chain in a TODGA and n-dodecane system. Determining the effect of chlorooctane and octane nitrile is important for understanding how phase modifier functional groups and their hydrogen bonding interactions affect Ln extraction. Through combining distribution ratio measurements with organic phase spectroscopic investigations, the impact of chlorooctane and octane nitrile on Ln extraction and their inner-sphere complexes is reported. The addition of either chlorooctane or octane nitrile to TODGA in n-dodecane decreases Ln extraction while maintaining the same inner-sphere Ln complex. The lack of change in inner-sphere Ln-TODGA coordination upon incorporation of phase modifiers and the significant impact of these phase modifiers on distribution ratios suggest the importance of a supramolecular structure. Understanding the role of chlorooctane and octane nitrile on the organic phase structure at longer length scales has been identified as an avenue for future investigations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Results from the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

The GCMS was part of the instrument complement on the Cassini-Huygens Probe to measure in situ the chemical composition of the atmosphere during the probe descent and coupled with the Aerosol Collector Pyrolyser (ACP) experiment by serving as detector for the pyrolization products to determine the composition of the aerosol particles. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. The GCMS collected data from an altitude of 146 km to ground impact. The Probe and the GCMS survived impact and collected data for 1 hour and 9 minutes on the surface. Mass spectra were collected during descent and on the ground over a range of m/z from 2 to 141. The major constituents of the lower atmosphere were confirmed to be NP and CH4. The methane mole fraction was uniform in the stratosphere. It increased below the tropopause, at about 32 km altitude, monotonically toward the surface, reaching a plateau at about 8 km at a level near saturation. After surface impact a steep increase of the methane signal was observed, suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. The measured mole fraction of Ar-40 is 4.3 x 10(exp-5) and of Ar-36 is 2.8 x 10(exp -7). The other primordial noble gases were below mole fraction. The isotope ratios of C-12/C-13 determined from methane measurements are 82.3 and of N-14/N-15 determined from molecular nitrogen are 183. The D/H isotope ratio determined from the H2 and HD measurements is 2.3 x l0(exp -4). Carbon dioxide, ethane, acetylene and cyanogen were detected evaporating from the surface in addition to methane.

Niemann, Hasso B.↗

Results from the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

The Gas Chromatograph Mass Spectrometer was one of six instruments on the Cassini-Huygens Probe mission to Titan. The GCMS measured in situ the chemical composition of the atmosphere during the probe descent and served as the detector for the pyrolization products for the Aerosol Collector Pyrolyser (ACP) experiment to determine the composition of the aerosol particles. The GCMS collected data from an altitude of 146 km to ground impact. The Probe and the GCMS survived impact and collected data for 1 hour and 9 minutes on the surface. Mass spectra were collected during descent and on the ground over a range of m/z from 2 to 141. The major constituents of the lower atmosphere were confirmed to be N2 and CH4. The methane mole fraction was uniform in the stratosphere. It increased below the tropopause, at about 32 km altitude, monotonically toward the surface, reaching a plateau at about 8 km at a level near saturation. After surface impact a steep increase of the methane signal was observed, suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. The measured mole fraction of Ar-40 is 4.3x10(exp -5) and of Ar-36 is 2.8x10(exp -7). The other primordial noble gases were below 10(exp -8) mole fraction. The isotope ratios of C-12/C-13 determined from methane measurements are 82.3 and of N-14/N-15 determined from molecular nitrogen are 183. The D/H isotope ratio determined from the H2 and HD measurements is 2.3x10(exp -4). Carbon dioxide, methane, acetylene and cyanogen were detected evaporating from the surface in addition to methane. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact.

Niemann, H.↗