Sensitivity of WRF/Chem simulated PM2.5 to initial/boundary conditions and planetary boundary layer parameterization schemes over the Indo-Gangetic Plain.

The ability of a chemical transport model to simulate accurate meteorological and chemical processes depends upon the physical parametrizations and quality of meteorological input data such as initial/boundary conditions. In this study, weather research and forecasting model coupled with chemistry (WRF-Chem) is used to test the sensitivity of PM2.5 predictions to planetary boundary layer (PBL) parameterization schemes (YSU, MYJ, MYNN, ACM2, and Boulac) and meteorological initial/boundary conditions (FNL, ERA-Interim, GDAS, and NCMRWF) over Indo-Gangetic Plain (Delhi, Punjab, Haryana, Uttar Pradesh, and Rajasthan) during the winter period (December 2017 to January 2018). The aim is to select the model configuration for simulating PM2.5 which shows the lowest errors and best agreement with the observed data. The best results were achieved with initial/boundary conditions from ERA and GDAS datasets and local PBL parameterization (MYJ and MYNN). It was also found that PM2.5 concentrations are relatively less sensitive to changes in initial/boundary conditions but in contrast show a stronger sensitivity to changes in the PBL scheme. Moreover, the sensitivity of the simulated PM2.5 to the choice of PBL scheme is more during the polluted hours of the day (evening to early morning), while that to the choice of the meteorological input data is more uniform and subdued over the day. This work indicates the optimal model setup in terms of choice of initial/boundary conditions datasets and PBL parameterization schemes for future air quality simulations. It also highlights the importance of the choice of PBL scheme over the choice of meteorological data set to the simulated PM2.5 by a chemical transport model.

Novel cinnamic acid analogues: synthesis of aminotroponyl acrylates by Pd(II)-catalysed C(sp2)-H olefination.

Cinnamic acid, a benzenoid scaffold, is a building block of various natural products. This report describes the synthesis of new non-benzenoid cinnamate analogs, 3-(6-amino-7-oxocyclohepta-1,3,5-trien-1-yl)acrylates, obtained through Pd(II)-catalyzed C7-H olefination of 2-aminotropones in the presence of acrylates. In these site-selective couplings, the troponyl-carbonyl function acts as a directing group. This strategy has been employed for the synthesis of new pseudopeptides from prolyl/prolamide containing aminotropone derivatives. These novel troponyl cinnamate analogs are potential precursors of hairpin forming peptides.

Pd-Catalyzed C(sp2)-H olefination: synthesis of N-alkylated isoindolinone scaffolds from aryl amides of amino acid esters.

Isoindolinone is a constituent of various natural products and synthetic biologically active compounds. The classical multi-step synthetic methods used to prepare various indolinone derivatives are tedious and challenging. One-pot synthetic methods are attractive and economical. Transition-metal-catalyzed C-H activation is an emerging tool for synthesizing natural products and small organic molecules via reducing the number of synthetic steps necessary. This paper describes the synthesis of N-alkyl-3-methenyl chiral isoindolinone derivatives from aryl amides of L-amino acids and non-activated alkene via Pd-catalyzed C(sp2)-H olefination. Herein, the amino acid residue acts as a directing group for olefination at the aryl ring, and then cyclization occurs at the amide NH. Hence, this methodology could be helpful to transform standard amino acids into respective chiral isoindolinone derivatives.

Unusual Pseudopeptides: Syntheses and Structural Analyses of Ethylenediprolyl Peptides and Their Metal Complexes with Cu(II) Ion.

The synthetic unnatural amino acids and their peptides as peptidomimetics have shown remarkable structural and functional properties. In the repertoire of synthetic peptides, pseudopeptides have emerged as attractive small peptidomimetics that are capable of forming the characteristic secondary structures in the solid/solution phase, as in natural peptides. This report describes the synthesis and structural analyses of novel pseudopeptides as ethylenediprolyl (etpro) tetra/hexapeptides, comprising a chiral diaminedicarboxylate scaffold. Their NMR and CD spectral analyses strongly support the formation of the ß-turn-type structures in organic solvents (ACN/MeOH). Further, the single-crystal X-ray studies of tetrapseudopeptide confirm the formation of a unique self-assembly structure as ß-strand type in the solid state through hydrogen bonding. Importantly, their diamine moiety influences the formation of Cu-complexes with Cu(II) ions. A tetrapseudopeptide monocarboxylate-Cu(II) complex forms the single crystal that is studied by the single-crystal X-ray diffractometer. The crystal structure of the tetrapseudopeptide-Cu(II) complex confirms the formation of the distorted square planar geometry structure, almost like the amyloid ß(Aß)-peptide-Cu(II) complex structural geometry. Hence, these etpro-pseudopeptides are emerging peptidomimatics that form ß-turn types of structures and metal complexes mainly with Cu(II) ions. These molecules could be considered for the development of peptide-based catalysts and peptide-based therapeutic drug candidates.

Performance of high resolution (400 m) PM2.5 forecast over Delhi.

This study reports a very high-resolution (400 m grid-spacing) operational air quality forecasting system developed to alert residents of Delhi and the National Capital Region (NCR) about forthcoming acute air pollution episodes. Such a high-resolution system has been developed for the first time and is evaluated during October 2019-February 2020. The system assimilates near real-time aerosol observations from in situ and space-borne platform in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) to produce a 72-h forecast daily in a dynamical downscaling framework. The assimilation of aerosol optical depth and surface PM2.5 observations improves the initial condition for surface PM2.5 by about 45 µg/m3 (about 50%).The accuracy of the forecast degrades slightly with lead time as mean bias increase from + 2.5 µg/m3 on the first day to - 17 µg/m3 on the third day of forecast. Our forecast is found to be very skillful both for PM2.5 concentration and unhealthy/ very unhealthy air quality index categories, and has been helping the decision-makers in Delhi make informed decisions.

Sub micron aerosol variability and its ageing process at a high altitude site in India: Impact of meteorological conditions.

The effect of relative humidity and temperature on the submicron aerosol variability and its ageing process was studied over a high altitude site, Mahabaleshwar in south-west India. The mass composition of non-refractory particulate matter of 1 µm (NR-PM1) size was obtained using Time of Flight Aerosol Chemical Speciation Monitor (ToF-ACSM) along with the measurements on a few trace gases during winter (December 2017-February 2018) and summer season (20th March - 5th May 2018). Sulfate exhibited strong dependence on the relative humidity (RH) as its mass fraction increased with the increase in RH. The Sulfate oxidation ratio (SOR) calculated during summer season also showed an increasing trend with RH indicating the influence of aqueous phase oxidation on sulfate fraction. On the other hand, OOA showed remarkable enhancement in its mass fraction with the increase in temperature along with the corresponding increase in f44 and tropospheric ozone. OOA, ozone and f44 ratio increased 14-34%, 8-26% and 25-43% respectively with the increase in temperature from 18 to 30 °C. This is indicative of the dominance of photochemical ageing processes during high temperature conditions. The extent of photochemical ageing was found to be higher during summer season (mean temperature ∼25.4 ± 2.6 °C) as compared to winter season (mean temperature ∼20.5 ± 2.6 °C). The nitrate diurnal was majorly governed by gas to particle partitioning process during winter season, whereas the summertime nitrate diurnal was influenced primarily by its formation rate. The non parametric wind regression analysis revealed that the mass concentration during winter was majorly contributed by distant sources from north east direction while during summer the local sources were more dominant.

How Much Does Large-Scale Crop Residue Burning Affect the Air Quality in Delhi?

Elevated PM2.5 concentrations frequently cause severe air pollution events in Delhi. Till recently, the effect of crop residue burning on the air quality in Delhi has not been fully quantified and the approaches to control the impact of fire emissions have not been effective. In this study, for the first time, we quantified the statewise contribution of post-monsoon crop residue burning in the northwestern states of India to surface PM2.5 concentrations in Delhi using several sensitivity experiments with the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) and FINNv1.5 fire emission inventory. Results were evaluated with ground-based observations in Delhi (21 stations), Punjab, and Haryana (14 stations). On average, ∼20% of PM2.5 concentration in Delhi during the post-monsoon season (October-November) was found to be contributed by nonlocal fire emissions. However, on typical air pollution events, fire emissions contributed as high as 50-75% (80-120 µg/m3) to PM2.5 in Delhi, highlighting the importance of both external transport and local emissions to PM2.5 pollution in Delhi.

Anomalous low tropospheric column ozone over eastern India during the severe drought event of monsoon 2002: a case study.

BACKGROUND, AIM, AND SCOPE: The present study is an attempt to examine some of the probable causes of the unusually low tropospheric column ozone observed over eastern India during the exceptional drought event in July 2002. METHOD: We examined horizontal wind and omega (vertical velocity) anomalies over the Indian region to understand the large-scale dynamical processes which prevailed in July 2002. We also examined anomalies in tropospheric carbon monoxide (CO), an important ozone precursor, and observed low CO mixing ratio in the free troposphere in 2002 over eastern India. RESULTS AND DISCUSSION: It was found that instead of a normal large-scale ascent, the air was descending in the middle and lower troposphere over a vast part of India. This configuration was apparently responsible for the less convective upwelling of precursors and likely caused less photochemical ozone formation in the free troposphere over eastern India in July 2002. CONCLUSION: The insight gained from this case study will hopefully provide a better understanding of the process controlling the distribution of the tropospheric ozone over the Indian region.