Investigation of Antisite Defect Formation and Chemical Expansion in LiNiPO4 by in Situ Neutron Diffraction

In situ neutron diffraction was used to characterize the effect of temperature on the crystal structure of LiNiPO4. LiNiPO4 adopts an ordered olivine structure at room temperature, but, with increasing temperature, this work shows that a significant amount of Li and Ni cation exchange occurs, for example, ∼15% at 900 °C. The antisite disorder is detected by residual nuclear densities on the M1 and M2 octahedral sites in the olivine structure using difference Fourier maps and by changes in cation site occupancies, lattice parameters, and mean ⟨M–O⟩ bond distances. The antisite disorder is also responsible for chemical expansion of the crystal lattice in addition to thermal expansion. Antisite defect formation at high temperature and its reversibility on cooling can be understood as an entropically driven feature of the crystal structure of LiNiPO4. The lithium ion diffusion pathway, that follows a curved trajectory along the b axis in the olivine structure, is, therefore, susceptible to be blocked if synthesis conditions are not carefully controlled and should also be influenced by the chemically expanded lattice of the disordered structure if this is preserved to ambient temperature by rapid cooling

The Air Pollution Human Health Burden in Different Future Scenarios That Involve the Mitigation of Near-Term Climate Forcers, Climate and Land-Use

Elevated surface concentrations of ozone and fine particulate matter (PM2.5) can lead to poor air quality and detrimental impacts on human health. These pollutants are also termed Near-Term Climate Forcers (NTCFs) as they can also influence the Earth's radiative balance on timescales shorter than long-lived greenhouse gases. Here we use the Earth system model, UKESM1, to simulate the change in surface ozone and PM2.5 concentrations from different NTCF mitigation scenarios, conducted as part of the Aerosol and Chemistry Model Intercomparison Project (AerChemMIP). These are then combined with relative risk estimates and projected changes in population demographics, to estimate the mortality burden attributable to long-term exposure to ambient air pollution. Scenarios that involve the strong mitigation of air pollutant emissions yield large future benefits to human health (25%), particularly across Asia for black carbon (7%), when compared to the future reference pathway. However, if anthropogenic emissions follow the reference pathway, then impacts to human health worsen over South Asia in the short term (11%) and across Africa (20%) in the longer term. Future climate change impacts on air pollutants can offset some of the health benefits achieved by emission mitigation measures over Europe for PM2.5 and East Asia for ozone. In addition, differences in the future chemical environment over regions are important considerations for mitigation measures to achieve the largest benefit to human health. Future policy measures to mitigate climate warming need to also consider the impact on air quality and human health across different regions to achieve the maximum co-benefits

Modeled response of ozone to electricity generation emissions in the northeastern United States using three sensitivity techniques

ABSTRACT: Electrical generation units (EGUs) are important sources of nitrogen oxides (NOx) that contribute to ozone air pollution. A dynamic management system can anticipate high ozone and dispatch EGU generation on a daily basis to attempt to avoid violations, temporarily scaling back or shutting down EGUs that most influence the high ozone while compensating for that generation elsewhere. Here we investigate the contributions of NOx from individual EGUs to high daily ozone, with the goal of informing the design of a dynamic management system. In particular, we illustrate the use of three sensitivity techniques in air quality models—brute force, decoupled direct method (DDM), and higher-order DDM—to quantify the sensitivity of high ozone to NOx emissions from 80 individual EGUs. We model two episodes with high ozone in the region around Pittsburgh, PA, on August 4 and 13, 2005, showing that the contribution of 80 EGUs to 8-hr daily maximum ozone ranges from 1 to >5 ppb at particular locations. At these locations and on the two high ozone days, shutting down power plants roughly 1.5 days before the 8-hr ozone violation causes greater ozone reductions than 1 full day before; however, the benefits of shutting down roughly 2 days before the high ozone are modest compared with 1.5 days. Using DDM, we find that six EGUs are responsible for >65% of the total EGU ozone contribution at locations of interest; in some locations, a single EGU is responsible for most of the contribution. Considering ozone sensitivities for all 80 EGUs, DDM performs well compared with a brute-force simulation with a small normalized mean bias (–0.20), while this bias is reduced when using the higher-order DDM (–0.10). Implications: Dynamic management of electrical generation has the potential to meet daily ozone air quality standards at low cost. We show that dynamic management can be effective at reducing ozone, as EGU contributions are important and as the number of EGUs that contribute to high ozone in a given location is small (<6). For two high ozone days and seven geographic regions, EGUs would best be shut down or their production scaled back roughly 1.5 days before the forecasted exceedance. Including online sensitivity techniques in an air quality forecasting model can provide timely and useful information on which EGUs would be most beneficial to shut down or scale back temporarily

Holographic analysis of diffraction structure factors

We combine the theory of inside-source/inside-detector x-ray fluorescence holography and Kossel lines/x ray standing waves in kinematic approximation to directly obtain the phases of the diffraction structure factors. The influence of Kossel lines and standing waves on holography is also discussed. We obtain partial phase determination from experimental data obtaining the sign of the real part of the structure factor for several reciprocal lattice vectors of a vanadium crystal.Comment: 4 pages, 3 figures, submitte

Estimating Wildfire Smoke Concentrations during the October 2017 California Fires through BME Space/Time Data Fusion of Observed, Modeled, and Satellite-Derived PM2.5

Exposure to wildfire smoke causes adverse health outcomes, suggesting the importance of accurately estimating smoke concentrations. Geostatistical methods can combine observed, modeled, and satellite-derived concentrations to produce accurate estimates. Here, we estimate daily average ground-level PM2.5 concentrations at a 1 km resolution during the October 2017 California wildfires, using the Constant Air Quality Model Performance (CAMP) and Bayesian Maximum Entropy (BME) methods to bias-correct and fuse three concentration datasets: permanent and temporary monitoring stations, a chemical transport model (CTM), and satellite-derived estimates. Four BME space/time kriging and data fusion methods were evaluated. All BME methods produce more accurate estimates than the standalone CTM and satellite products. Adding temporary station data increases the R2 by 36%. The data fusion of observations with the CAMP-corrected CTM and satellite-derived concentrations provides the best estimate (R2 = 0.713) in fire-impacted regions, emphasizing the importance of combining multiple datasets. We estimate that approximately 65,000 people were exposed to very unhealthy air (daily average PM2.5 ≥ 150.5 μg/m3)

An Anglo-Saxon execution cemetery at Walkington Wold, Yorkshire

This paper presents a re-evaluation of a cemetery excavated over 30 years ago at Walkington Wold in east Yorkshire. The cemetery is characterized by careless burial on diverse alignments, and by the fact that most of the skeletons did not have associated crania. The cemetery has been variously described as being the result of an early post-Roman massacre, as providing evidence for a ‘Celtic’ head cult or as an Anglo-Saxon execution cemetery. In order to resolve the matter, radiocarbon dates were acquired and a re-examination of the skeletal remains was undertaken. It was confirmed that the cemetery was an Anglo-Saxon execution cemetery, the only known example from northern England, and the site is set into its wider context in the paper

Heavy quarkonium 2S states in light-front quark model

We study the charmonium 2S states $\psi'$ and $\eta_c'$, and the bottomonium 2S states $\Upsilon'$ and $\eta_b'$, using the light-front quark model and the 2S state wave function of harmonic oscillator as the approximation of the 2S quarkonium wave function. The decay constants, transition form factors and masses of these mesons are calculated and compared with experimental data. Predictions of quantities such as Br$(\psi' \to \gamma \eta_c')$ are made. The 2S wave function may help us learn more about the structure of these heavy quarkonia.Comment: 5 latex pages, final version for journal publicatio