Identification of sources of coarse mode aerosol particles (PM10) using ATR-FTIR and SEM-EDX spectroscopy over the Himalayan Region of India.

This study attempts to examine the morphological, elemental and physical characteristics of PM10 over the Indian Himalayan Region (IHR) using FTIR and scanning electron microscopy-energy dispersive X-ray (SEM-EDX) analysis. The study aimed at source identification of PM10 by exploring the inorganic ions, organic functional groups, morphology and elemental characteristics. The pollution load of PM10 was estimated as 63 ± 22 µg m-3; 53 ± 16 µg m-3; 67 ± 26 µg m-3 and 55 ± 11 µg m-3 over Mohal-Kullu, Almora, Nainital and Darjeeling, respectively. ATR-FTIR spectrum analysis revealed the existence of inorganic ions (SiO44-, TiO2, SO42-, SO3-, NO3-, NO2-, CO32-, HCO3-, NH4+) and organic functional groups (C-C, C-H, C=C, C≡C, C=O, N-H, C≡N, C=N, O-H, cyclic rings, aromatic compounds and some heterogeneous groups) in PM10 which may arise from geogenic, biogenic and anthropogenic sources. The morphological and elemental characterization was performed by SEM-EDX, inferring for geogenic origin (Al, Na, K, Ca, Mg and Fe) due to the presence of different morphologies (irregular, spherical, cluster, sheet-like solid deposition and columnar). In contrast, particles having biogenic and anthropogenic origins (K, S and Ba) have primarily spherical with few irregular particles at all the study sites. Also, the statistical analysis ANOVA depicts that among all the detected elements, Na, Al, Si, S and K are site-specific in nature as their mean of aw% significantly varied for all the sites. The trajectory analysis revealed that the Uttarakhand, Jammu and Kashmir, the Thar Desert, Himachal Pradesh, Pakistan, Afghanistan, Nepal, Sikkim, the Indo-Gangetic Plain (IGP) and the Bay of Bengal (BoB) contribute to the increased loading of atmospheric pollutants in various locations within the IHR.

Ionic Covalent Organic Framework as a Dual Functional Sensor for Temperature and Humidity.

Visual sensing of humidity and temperature by solids plays an important role in the everyday life and in industrial processes. Due to their hydrophobic nature, most covalent organic framework (COF) sensors often exhibit poor optical response when exposed to moisture. To overcome this challenge, the optical response is set out to improve, to moisture by incorporating H-bonding ionic functionalities into the COF network. A highly sensitive COF, consisting of guanidinium and diformylpyridine linkers (TG-DFP), capable of detecting changes in temperature and moisture content is fabricated. The hydrophilic nature of the framework enables enhanced water uptake, allowing the trapped water molecules to form a large number of hydrogen bonds. Despite the presence of non-emissive building blocks, the H-bonds restrict internal bond rotation within the COF, leading to reversible fluorescence and solid-state optical hydrochromism in response to relative humidity and temperature.

Chemical characteristics, morphology and source apportionment of PM10 over National Capital Region (NCR) of India.

The present study frames the physico-chemical characteristics and the source apportionment of PM10 over National Capital Region (NCR) of India using the receptor model's Positive Matrix Factorization (PMF) and Principal Momponent Mnalysis/Absolute Principal Component Score-Multilinear Regression (PCA/APCS-MLR). The annual average mass concentration of PM10 over the urban site of Faridabad, IGDTUW-Delhi and CSIR-NPL of NCR-Delhi were observed to be 195 ± 121, 275 ± 141 and 209 ± 81 µg m-3, respectively. Carbonaceous species (organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC)), elemental constituents (Al, Ti, Na, Mg, Cr, Mn, Fe, Cu, Zn, Br, Ba, Mo Pb) and water-soluble ionic components (F-, Cl-, SO42-, NO3-, NH4+, Na+, K+, Mg2+, Ca2+) of PM10 were entrenched to the receptor models to comprehend the possible sources of PM10. The PMF assorted sources over Faridabad were soil dust (SD 15%), industrial emission (IE 14%), vehicular emission (VE 19%), secondary aerosol (SA 23%) and sodium magnesium salt (SMS 17%). For IGDTUW-Delhi, the sources were SD (16%), VE (19%), SMS (18%), IE (11%), SA (27%) and VE + IE (9%). Emission sources like SD (24%), IE (8%), SMS (20%), VE + IE (12%), VE (15%) and SA + BB (21%) were extracted over CSIR-NPL, New Delhi, which are quite obvious towards the sites. PCA/APCS-MLR quantified the similar sources with varied percentage contribution. Additionally, catalogue the Conditional Bivariate Probability Function (CBPF) for directionality of the local source regions and morphology as spherical, flocculent and irregular were imaged using a Field Emission-Scanning Electron Microscope (FE-SEM).

Emission inventory of inorganic trace gases from solid residential fuels over the National Capital Territory of India.

In developing nations, solid residential fuels are the major sources of primary energy for various domestic activities. To date, the emission inventory of inorganic trace gases over National Capital Territory (NCT) was prepared using either default or country-specific emission factors. In this paper, we report (for the first time) the spatial variation of emission factors (EFs) of inorganic trace gases (SO2, NO, NO2, CO, CO2, and CH4) from the residential fuels used in slums and rural areas of NCT determined using dilution chamber in the laboratory. 147 residential fuel samples, including fuelwood, dung cake, crop residues, coal, etc., were collected at 149 NCT locations out of 675 slum clusters and 146 rural villages. The range of EF(s) of SO2 (0.02 ± 0.01 to 0.04 ± 0.01 g kg-1), CH4 (0.10 to 0.34 g kg-1), NO2 (0.01 to 0.02 g kg-1) is lower than the CO (3.55 ± 1.72 to 6.07 ± 1.53 g kg-1) and CO2 (0 to 129.45 ± 46.94 g kg-1). The north and north west districts of NCT are emission hotspots for CH4, NO, and NO2 emissions, whereas, the southern and northern areas of NCT are for CO2. These citywide emission inventories (0.05° × 0.05°) of inorganic trace gases are prepared using laboratory-determined EFs and available consumption data determined by recent survey information. Among solid residential fuels, fuel wood, and dung cake are two major contributors to inorganic trace gases in NCT.

Health risk assessment of aerosol particles (PM2.5 and PM10) during winter crop at the agricultural site of Delhi, India.

For the last few decades, air pollution in developing country like India is increasing, and it is a matter of huge concern due to its associated human health impacts. In this region, the burgeoning population, escalating urbanization and industrialization, has been cited as the major reason for such a high air pollution. The present study was carried out for health risk assessment of aerosol particles (PM10 and PM2.5) and its associated heavy metals of an agriculture farm site at Indian Agricultural Research Institute (IARI) considered to be green urban area in Delhi, India. The concentrations of both PM10 and PM2.5 varied significantly from 136 to 177 µg/m3 and 56 to 162 µg/m3, respectively at the site. In the present case, the highest PM10 and PM2.5 levels were reported in January, followed by December. The levels of ambient PM10 and PM2.5 are influenced by wind prevailing meteorology. These levels of PM10 and PM2.5 are more than the permissible limits of WHO guidelines of 15 and 5 µg/m3, respectively, thereby leading to high aerosol loadings specifically in winters. The PM concentration of the atmosphere was found to be negatively correlated with temperature during the sampling period. The concentrations of surface ozone O3 and NOx in the present study were observed to be high in February and March, respectively. The increasing air pollution in the city of Delhi poses a great risk to the human health, as the particulate matter loaded with heavy metals can enter humans via different pathways, viz., ingestion, inhalation, and absorption through skin. The mean hazard index for metals (Zn, Pb, Cd, As, Cr, and Ni) was observed within the acceptable limit (HI < 1), thereby indicating negligible non-carcinogenic effects to residing population. The carcinogenic risk assessment was conducted for Cd, Pb, and As only, as the concentrations for other metals were found to be quite low. The carcinogenic risk values were also within the limits of USEPA standards, indicating no carcinogenic risks to the health of children and adults residing near the site. This information about the PM pollution at the agricultural site and health risk assessment will serve as a baseline data in assessment of human health impacts due to air pollution at the local scale and can be used for development of mitigation strategies for tackling air pollution.

Light-driven self-assembly of spiropyran-functionalized covalent organic framework.

Controlling the number of molecular switches and their relative positioning within porous materials is critical to their functionality and properties. The proximity of many molecular switches to one another can hinder or completely suppress their response. Herein, a synthetic strategy involving mixed linkers is used to control the distribution of spiropyran-functionalized linkers in a covalent organic framework (COF). The COF contains a spiropyran in each pore which exhibits excellent reversible photoswitching behavior to its merocyanine form in the solid state in response to UV/Vis light. The spiro-COF possesses an urchin-shaped morphology and exhibits a morphological transition to 2D nanosheets and vesicles in solution upon UV light irradiation. The merocyanine-equipped COFs are extremely stable and possess a more ordered structure with enhanced photoluminescence. This approach to modulating structural isomerization in the solid state is used to develop inkless printing media, while the photomediated polarity change is used for water harvesting applications.

Role of South Asian outflow on the oxidative potential of marine aerosols over the Indian Ocean.

Oxidative potential (OP) of fine marine aerosols (PM2.5) over the northern Indian Ocean (N_IO) and equatorial Indian Ocean (E_IO) were studied using shipborne measurements conducted as part of the Integrated Campaign for Aerosols, gases and Radiation Budget (ICARB-2018). During the study, an enhanced concentration of PM2.5 was found over N_IO (27.22 ± 14.29 µg.m-3) compared with E_IO (15.91 ± 2.58 µg.m-3), as N_IO experiences continental outflow from anthropogenically dominated South Asian region. However, E_IO received pristine air masses from the middle of the Arabian Sea, implying a reduced concentration. The OP of PM2.5 was evaluated using a dithiothreitol (DTT) assay. The mass (DTTm or intrinsic OP) and volume (DTTv or extrinsic OP) normalized DTT exhibited a significant spatial variation over the Indian Ocean (IO). Intrinsic OP showed ∼2 times higher values over N_IO than E_IO, indicating aging of aerosols during long-range transport impacts OP of marine aerosol. Similarly, increased concentrations of anthropogenic species such as non-sea sulfate (nssSO42-), nitrate (NO3-), ammonium (NH4+), non-sea potassium ion (nssK+), water-soluble transition metals (Fe, Ti, Zn, Cu, Mn, Cr), elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC), were also observed over N_IO compared with E_IO. Pearson correlation and multiple linear regression (MLR) analysis revealed that combustion sources, chemical processing and co-transportation of anthropogenic species during long-range transport are the main drivers of intrinsic OP in the outflow region.

Synthesis of Self-Assembled Single Atomic Layer Gold Crystals-Goldene.

We report, for the first time, a technique to synthesize free-standing, one-atom thick 2D gold crystals (namely, goldene) and self-assembled 2D periodic arrays of goldene. High-resolution transmission electron microscopy (HRTEM) imaging of goldene revealed herringbone and honeycomb lattices, which are primarily gold surface features due to its reconstruction. Imaging of these surface-only features by a nonsurface characterization technique such as HRTEM is an unequivocal proof of the absence of three-dimensionality in goldene. Atomic force microscopy confirmed 1-2 Šthickness of goldene. High-resolution X-ray photoelectron spectroscopy (HR-XPS), selective area electron diffraction, and energy-dispersive X-ray spectroscopy confirmed the chemical identity of goldene. We discovered the phenomenon of electric field-induced self-assembly of goldene supracrystals with a herringbone structure and developed an electric field printing (e-print) technique for goldene arrays. Goldene showed a semiconductor response with a knee voltage of ∼3.2 V, and I/V spectroscopy revealed periodic room temperature Coulomb blockade oscillations. These observations are consistent with the theoretical calculations reported in the literature predicting enhanced Coulombic interactions between gold valence electrons and the nucleus in stable 2D gold. Goldene exhibited multiple, intense, and well-resolved optical absorption peaks and several fine bands across the UV-vis region, and we calculated its optical band gap to be 3.59 eV. Magnetic force microscopy measurements of goldene periodic arrays showed a ∼5 mV peak amplitude confirming its ferromagnetism. Optical and magnetic properties of goldene are consistent with those reported in the literature for 2D planar gold clusters with less than 12 atoms.

Fluorescence turn on amine detection in a cationic covalent organic framework.

Ionic covalent organic frameworks (iCOFs) are new examples of porous materials and have shown great potential for various applications. When functionalized with suitable emission sites, guest uptake via the ionic moieties of iCOFs can cause a significant change in luminescence, making them excellent candidates for chemosensors. In here, we present a luminescence sensor in the form of an ionic covalent organic framework (TGH+•PD) composed of guanidinium and phenanthroline moieties for the detection of ammonia and primary aliphatic amines. TGH+•PD exhibits strong emission enhancement in the presence of selective primary amines due to the suppression of intramolecular charge transfer (ICT) with an ultra-low detection limit of 1.2 × 10‒7 M for ammonia. The presence of ionic moieties makes TGH+•PD highly dispersible in water, while deprotonation of the guanidinium moiety by amines restricts its ICT process and signals their presence by enhanced fluorescence emission. The presence of ordered pore walls introduces size selectivity among analyte molecules, and the iCOF has been successfully used to monitor meat products that release biogenic amine vapors upon decomposition due to improper storage.

Association between Acute Exposure to PM2.5 Chemical Species and Mortality in Megacity Delhi, India.

The association between daily all-cause mortality and short-term fine particulate matter (PM2.5) exposure is well established in the literature. However, association between acute exposure to PM2.5 chemical species and mortality is not well known, especially in developing countries like India. Here we examined associations between mortality and acute exposure to PM2.5 mass concentration and their 15 chemical components using data from 2013 to 2016 in megacity Delhi using a semiparametric quasi-Poisson regression model, adjusting for mean temperature, relative humidity, and long-term time trend as the major potential confounders. Mortality estimates were further checked for effect modification by sex, age group, and season. The subspecies of NO3-, NH4NO3, Cr, NH4+, EC, and OC showed a higher mortality impact than the total PM2.5 mass. Males were at higher risk from NO3-, SO42-, and their NH4+ compounds along with carcinogen Cr, whereas female group was at higher risk from EC and OC. Among all age groups, the elderly above 65 years were the most vulnerable group prone to mortality effects from maximum species. The major mortality risk from all hazardous species arose from their winter exposures. Our study provides the first evidence of association between acute exposure to PM2.5 chemical species and mortality anywhere in India and recommends similar studies in other regions so that sectoral mitigation emitting the most toxic species can be prioritized to maximize the health benefits.

Chemical properties of emissions from solid residential fuels used for energy in the rural sector of the southern region of India.

In the present study, we have estimated the emission factors (EFs) of particulate matter (PM), organic and elemental carbon (OC and EC), oxide of sulfur and nitrogen, and water-soluble ionic species emitted from residential fuels (fuelwood, crop residue, dung cake) used in the rural sector of five states (Kerala, Karnataka, Andhra Pradesh, Telangana, Tamil Nadu) of the southern region of India. Average EFs of PM, OC, and EC from fuelwood (FW), crop residues (CR), and dung cakes (DC) from southern region of India are estimated as follows: PM: 6.35 ± 5.64 g/kg (FW), 6.99 ± 5.46 g/kg (CR), 9.69 ± 3.73 g/kg (DC); OC: 1.60 ± 1.72 g/kg (FW), 1.50 ± 1.52 g/kg (CR), 3.54 ± 0.75 g/kg (DC); and EC: 0.46 ± 0.53 g/kg (FW), 0.29 ± 0.17 g/kg (CR), 0.21 ± 0.11 g/kg (DC), respectively. Similarly, the average EFs of SO2, NOx from FW, CR, and DC are determined to be as follows: SO2: 0.40 ± 0.37 g/kg (FW), 1.17 ± 0.25 g/kg (CR), and 0.18 ± 0.10 g/kg (DC); NOx: 1.11 ± 1.22 g/kg (FW), 0.69 ± 0.37 g/kg (CR), and 0.91 ± 0.54 g/kg (DC), respectively. PO43- shows the highest EF from FW (646.02 ± 576.35 mg/kg), CR (531.06 ± 678.29 mg/kg) among all anions followed by Cl- (FW: 512.91 ± 700.35 mg/kg, CR: 661.61 ± 865.46 mg/kg and DC: 104.16 ± 54.01 mg/kg); whereas, Na+ shows highest EF from FW (254.05 ± 298.50 mg/kg) and CR (249.36 ± 294.85 mg/kg) among all cations. The total emissions of trace gases, PM, and their chemical composition from FW, CR, and DC have been calculated using laboratory-generated EFs over the southern region of India. CR (1595.58 ± 14.24 Gg) contributes to higher emission of PM as compared to FW (218.78 ± 53.93 Gg), whereas the contribution from DC is negligible.

Gridded distribution of total suspended particulate matter (TSP) and their chemical characterization over Delhi during winter.

In the present study, total suspended particulate matter (TSP) samples were collected at 47 different sites (47 grids of 5 × 5 km2 area) of Delhi during winter (January-February 2019) in campaign mode. To understand the spatial variation of sources, TSP samples were analyzed for chemical compositions including carbonaceous species [organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC)], water-soluble total nitrogen (WSTN), water-soluble inorganic nitrogen (WSIN), polycyclic aromatic hydrocarbons (16 PAHs), water-soluble inorganic species (WSIS) (F-, Cl-, SO42-, NO2-, NO3-, PO43-, NH4+, Ca2+, Mg2+, Na+, and K+), and major and minor trace elements (B, Na, Mg, Al, P, S, Cl, K, Ca, Ti, Fe, Zn, Cr, Mn, Cu, As, Pd, F, and Ag). During the campaign, the maximum concentration of several components of TSP (996 µg/m3) was recorded at the Rana Pratap Bagh area, representing a pollution hotspot of Delhi. The maximum concentrations of PAHs were recorded at Udhyog Nagar, a region close to heavily loaded diesel vehicles, small rubber factories, and waste burning areas. Higher content of Cl- and Cl-/Na+ ratio (>1.7) suggests the presence of nonmarine anthropogenic sources of Cl- over Delhi. Minimum concentrations of OC, EC, WSOC, PAHs, and WSIS in TSP were observed at Kalkaji, representing the least polluted area in Delhi. Enrichment factor <5.0 at several locations and a significant correlation of Al with Mg, Fe, Ti, and Ca and C/N ratio indicated the abundance of mineral/crustal dust in TSP over Delhi. Principal component analysis (PCA) was also performed for the source apportionment of TSP, and extracted soil dust was found to be the major contributor to TSP, followed by biomass burning, open waste burning, secondary aerosol, and vehicular emissions.

Frequency distribution of pollutant concentrations over Indian megacities impacted by the COVID-19 lockdown.

The megacities experience poor air quality frequently due to stronger anthropogenic emissions. India had one of the longest lockdowns in 2020 to curb the spread of COVID-19, leading to reductions in the emissions from anthropogenic activities. In this article, the frequency distributions of different pollutants have been analysed over two densely populated megacities: Delhi (28.70° N; 77.10° E) and Kolkata (22.57° N; 88.36° E). In Delhi, the percentage of days with PM2.5 levels exceeding the National Ambient Air Quality Standards (NAAQS) between 25 March and 17 June dropped from 98% in 2019 to 61% in 2020. The lockdown phase 1 brought down the PM10 (particulate matter having an aerodynamic diameter ≤ 10 µm) levels below the daily NAAQS limit over Delhi and Kolkata. However, PM10 exceeded the limit of 100 µgm-3 during phases 2-5 of lockdown over Delhi due to lower temperature, weaker winds, increased relative humidity and commencement of limited traffic movement. The PM2.5 levels exhibit a regressive trend in the highest range from the year 2019 to 2020 in Delhi. The daily mean value for PM2.5 concentrations dropped from 85-90 µgm-3 to 40-45 µgm-3 bin, whereas the PM10 levels witnessed a reduction from 160-180 µgm-3 to 100-120 µgm-3 bin due to the lockdown. Kolkata also experienced a shift in the peak of PM10 distribution from 80-100 µgm-3 in 2019 to 20-40 µgm-3 during the lockdown. The PM2.5 levels in peak frequency distribution were recorded in the 35-40 µgm-3 bin in 2019 which dropped to 15-20 µgm-3 in 2020. In line with particulate matter, other primary gaseous pollutants (NOx, CO, SO2, NH3) also showed decline. However, changes in O3 showed mixed trends with enhancements in some of the phases and reductions in other phases. In contrast to daily mean O3, 8-h maximum O3 showed a reduction over Delhi during lockdown phases except for phase 3. Interestingly, the time of daily maximum was observed to be delayed by ~ 2 h over Delhi (from 1300 to 1500 h) and ~ 1 h over Kolkata (from 1300 to 1400 h) almost coinciding with the time of maximum temperature, highlighting the role of meteorology versus precursors. Emission reductions weakened the chemical sink of O3 leading to enhancement (120%; 11 ppbv) in night-time O3 over Delhi during phases 1-3.

Seasonal variations in carbonaceous species of PM2.5 aerosols at an urban location situated in Indo-Gangetic Plain and its relationship with transport pathways, including the potential sources.

The study examines the variation in organic carbon (OC) and elemental carbon (EC) in PM2.5 concentration at an urban location of Indo-Gangetic Plains (IGP) to understand the impact of seasonality and regional crop residue burning activities. Seasonal cluster analysis of backward air masses and concentration-weighted trajectory (CWT) analysis was performed to identify seasonal transport pathways and potential source regions of carbonaceous aerosols. The mean PM2.5 level during the study period was 57 ± 41.6 µgm-3 (5.0-187.3 µgm-3), whereas OC and EC concentration ranges from 2.8 µgm-3 to 28.2 µgm-3 and 1.3 µgm-3 to 15.5 µgm-3 with a mean value of 8.4 ± 5.5 µgm-3 and 5.1 ± 3.3 µgm-3 respectively. The highest mean PM2.5 concentration was found during the winter season (111.3 ± 25.5 µgm-3), which rises 3.6 times compared to the monsoon season. OC and EC also follow a similar trend having the highest levels in winter. Total carbonaceous aerosols contribute ∼38% of PM2.5 composition. The positive linear trend between OC and EC identified the key sources. HYSPLIT cluster analysis of backward air mass trajectories revealed that during the post-monsoon, winters, pre-monsoon, and monsoon, 71%, 81%, 60%, and 43% of air masses originate within the 500 km radius of IGP. CWT analysis and abundance of OC in post-monsoon and winters season establish a linkage between regional solid-biomass fuel use and crop residue burning activities, including meteorology. Moreover, the low annual average OC/EC ratio (1.75) indicates the overall influence of vehicular emissions. The current dataset of carbonaceous aerosols collated with other Indian studies could be used to validate the global aerosol models on a regional scale and aid in evidence-based air pollution reduction strategies.

Drivers of air pollution variability during second wave of COVID-19 in Delhi, India.

To curb the 2nd wave of COVID-19 disease in April-May 2021, a night curfew followed by full lockdown was imposed over the National Capital Territory, Delhi. We have analyzed the observed variation in pollutants and meteorology, and role of local and transboundary emission sources during night-curfew and lockdown, as compared to pre-lockdown period and identical periods of 2020 lockdown as well as of 2018 and 2019. In 2021, concentration of pollutants (except O3, SO2, and toluene) declined by 4-16% during night-curfew as compared to the pre-lockdown period but these changes are not statistically significant. During lockdown in 2021, various pollutants decreased by 1-28% as compared to the night-curfew (except O3 and PM2.5), but increased by 31-129% compared to the identical period of 2020 lockdown except O3. Advection of pollutants from the region of moderate lockdown restrictions and an abrupt increase in crop-residue burning activity (120-587%) over Haryana and Punjab increased the air pollution levels over NCT during the lockdown period of 2021 as compared to 2020 in addition to a significant contribution of long-range transport. The increase in PM2.5 during the lockdown period of 2021 compared to 2020 might led to 5-29 additional premature mortalities.

In vivo oral insulin delivery via covalent organic frameworks.

With diabetes being the 7th leading cause of death worldwide, overcoming issues limiting the oral administration of insulin is of global significance. The development of imine-linked-covalent organic framework (nCOF) nanoparticles for oral insulin delivery to overcome these delivery barriers is herein reported. A gastro-resistant nCOF was prepared from layered nanosheets with insulin loaded between the nanosheet layers. The insulin-loaded nCOF exhibited insulin protection in digestive fluids in vitro as well as glucose-responsive release, and this hyperglycemia-induced release was confirmed in vivo in diabetic rats without noticeable toxic effects. This is strong evidence that nCOF-based oral insulin delivery systems could replace traditional subcutaneous injections easing insulin therapy.

Seasonal variation and sources of carbonaceous species and elements in PM2.5 and PM10 over the eastern Himalaya.

The study represents the seasonal characteristics (carbonaceous aerosols and elements) and the contribution of prominent sources of PM2.5 and PM10 in the high altitude of the eastern Himalaya (Darjeeling) during August 2018-July 2019. Carbonaceous aerosols [organic carbon (OC), elemental carbon (EC), and water soluble organic carbon (WSOC)] and elements (Al, Fe, Ti, Cu, Zn, Mn, Cr, Ni, Mo, Cl, P, S, K, Zr, Pb, Na, Mg, Ca, and B) in PM2.5 and PM10 were analyzed to estimate their possible sources. The annual concentrations of PM2.5 and PM10 were computed as 37±12 µg m-3 and 58±18 µg m-3, respectively. In the present case, total carbonaceous species in PM2.5 and PM10 were accounted for 20.6% of PM2.5 and 18.6% of PM10, respectively, whereas trace elements in PM2.5 and PM10 were estimated to be 15% of PM2.5 and 12% of PM10, respectively. Monthly and seasonal variations in mass concentrations of carbonaceous aerosols and elements in PM2.5 and PM10 were also observed during the observational period. In PM2.5, the annual concentrations of POC and SOC were 2.35 ± 1.06 µg m-3 (66% of OC) and 1.19±0.57 µg m-3 (34% of OC), respectively, whereas annual average POC and SOC concentrations in PM10 were 3.18 ± 1.13 µg m-3 (63% of OC) and 2.05±0.98 µg m-3 (37% of OC), respectively. The seasonal contribution of POC and SOC were ranging from 55 to 77% and 33 to 45% of OC in PM2.5, respectively, whereas in PM10, the seasonal contributions of POC and SOC were ranging from 51 to 73% and 37 to 49% of OC, respectively. The positive relationship between OC & EC and OC & WSOC of PM2.5 and PM10 during all the seasons (except monsoon in case of PM10) indicates their common sources. The enrichment factors (EFs) and significant positive correlation of Al with othe crustal elements (Fe, Ca, Mg, and Ti) of fine and coarse mode aerosols indicate the influence of mineral dust at Darjeeling. Principal component analysis (PCA) resolved the four common sources (biomass burning + fossil fuel combustion (BB + FFC), crustal/soil dust, vehicular emissions (VE), and industrial emissions (IE)) of PM2.5 and PM10 in Darjeeling.

Taming the Topology of Calix[4]arene-Based 2D-Covalent Organic Frameworks: Interpenetrated vs Noninterpenetrated Frameworks and Their Selective Removal of Cationic Dyes.

A bowl-shaped calix[4]arene with its exciting host-guest chemistry is a versatile supramolecular building block for the synthesis of distinct coordination cages or metal-organic frameworks. However, its utility in the synthesis of crystalline covalent organic frameworks (COFs) remains challenging, presumably due to its conformational flexibility. Here, we report the synthesis of a periodic 2D extended organic network of calix[4]arenes joined by a linear benzidine linker via dynamic imine bonds. By tuning the interaction among neighboring calixarene units through varying the concentration in the reaction mixture, we show the selective formation of interpenetrated (CX4-BD-1) and non-interpenetrated (CX4-BD-2) frameworks. The cone-shaped calixarene moiety in the structural backbone allows for the interweaving of two neighboring layers in CX4-BD-1, making it a unique example of interpenetrated 2D layers. Due to the high negative surface charge from calixarene units, both COFs have shown high performance in charge-selective dye removal and an exceptional selectivity for cationic dyes irrespective of their molecular size. The charge distribution of the COFs and the resulting selectivity for the cationic dyes were further investigated using computational methods.

Investigating the seasonal variability in source contribution to PM2.5 and PM10 using different receptor models during 2013-2016 in Delhi, India.

The present work deals with the seasonal variations in the contribution of sources to PM2.5 and PM10 in Delhi, India. Samples of PM2.5 and PM10 were collected from January 2013 to December 2016 at an urban site of Delhi, India, and analyzed to evaluate their chemical components [organic carbon (OC), elemental carbon (EC), water-soluble inorganic components (WSICs), and major and trace elements]. The average concentrations of PM2.5 and PM10 were 131 ± 79 µg m-3 and 238 ± 106 µg m-3, respectively during the entire sampling period. The analyzed and seasonally segregated data sets of both PM2.5 and PM10 were used as input in the three different receptor models, i.e., principal component analysis-absolute principal component score (PCA-APCS), UNMIX, and positive matrix factorization (PMF), to achieve conjointly corroborated results. The present study deals with the implementation and comparison of results of three different multivariate receptor models (PCA-APCS, UNMIX, and PMF) on the same data sets that allowed a better understanding of the probable sources of PM2.5 and PM10 as well as the comportment of these sources with respect to different seasons. PCA-APCS, UNMIX, and PMF extracted similar sources but in different contributions to PM2.5 and PM10. All the three models extracted 7 similar sources while mutually confirmed the 4 major sources over Delhi, i.e., secondary aerosols, vehicular emissions, biomass burning, and soil dust, although the contribution of these sources varies seasonally. PCA-APCS and UNMIX analysis identified a less number of sources (besides mixed type) as compared to the PMF, which may cause erroneous interpretation of seasonal implications on source contribution to the PM mass concentration.

Covalent Organic Framework Embedded with Magnetic Nanoparticles for MRI and Chemo-Thermotherapy.

Nanoscale imine-linked covalent organic frameworks (nCOFs) were first loaded with the anticancer drug Doxorubicin (Dox), coated with magnetic iron oxide nanoparticles (γ-Fe2O3 NPs), and stabilized with a shell of poly(l-lysine) cationic polymer (PLL) for simultaneous synergistic thermo-chemotherapy treatment and MRI imaging. The pH responsivity of the resulting nanoagents (γ-SD/PLL) allowed the release of the drug selectively within the acidic microenvironment of late endosomes and lysosomes of cancer cells (pH 5.4) and not in physiological conditions (pH 7.4). γ-SD/PLL could efficiently generate high heat (48 °C) upon exposure to an alternating magnetic field due to the nCOF porous structure that facilitates the heat conduction, making γ-SD/PLL excellent heat mediators in an aqueous solution. The drug-loaded magnetic nCOF composites were cytotoxic due to the synergistic toxicity of Dox and the effects of hyperthermia in vitro on glioblastoma U251-MG cells and in vivo on zebrafish embryos, but they were not significantly toxic to noncancerous cells (HEK293). To the best of our knowledge, this is the first report of multimodal MRI probe and chemo-thermotherapeutic magnetic nCOF composites.