A Siderophore Mimicking Gelation Component for Capturing and Self-Separation of Fe(III) from an Aqueous Solution of Mixture of Metal Ions.

The carbohydrazide-based gelation component N2,N4,N6-(1,3,5-triazine-2,4,6-triyl)tris(benzene-1,3,5-tricarbohydrazide) (CBTC) was synthesized and characterized using various spectroscopic tools. CBTC and trimesic acid (TMA) get self-assembled to form metallogel with Fe3+, specifically through various noncovalent interactions in a DMSO and H2O mixture. The self-assembly shows remarkable specificity toward Fe(III) among different transition metal salts. It is pertinent to point out that the binding specificity for Fe3+ can also be found in nature in the form of siderophores, as they are mainly involved in scavenging iron selectively from the surroundings. DFT studies have been used to investigate the possible interaction between the different components of the iron metallogel. To determine the selectivity of CBTC for iron, CBTC, along with trimesic acid, is used to interact with other metal ions, including Fe(III) ions, in a single system. The gelation components CBTC and TMA selectively bind with iron(III), which leads to the formation of metallogel and gets separated as a discrete layer, leaving the other metal ions in the solution. Therefore, CBTC and TMA together show iron-scavenging properties. This selective scavenging property is explored through FE-SEM, XPS, PXRD, IR, and ICP-AES analysis. The FE-SEM analysis shows a flower-petal-like morphology for the Fe(III) metallogel. The resemblance in the CBTC-TMA-Fe metallogel and metallogel obtained from the mixture of different metal salts is established through FE-SEM images and XPS analysis. The release of iron from the metallogel is achieved with the help of ascorbic acid, which converts Fe3+ to Fe2+. In biological systems, iron also gets released similarly from siderophores. This is the first report where the synthesized gelation component CBTC molecule is capable of scavenging out iron in the form of metallogel and self-separating from the aqueous mixture in the presence of various other metal ions.

Accumulation and risks of polycyclic aromatic hydrocarbons and trace metals in tropical urban soils.

The study deals with the combined contribution of polycyclic aromatic hydrocarbons (PAHs) and metals to health risk in Delhi soils. Surface soils (0-5 cm) collected from three different land-use regions (industrial, flood-plain and a reference site) in Delhi, India over a period of 1 year were characterized with respect to 16 US Environmental Protection Agency priority PAHs and five trace metals (Zn, Fe, Ni, Cr and Cd). Mean annual ∑16PAH concentrations at the industrial and flood-plain sites (10,893.2 ± 2826.4 and 3075.4 ± 948.7 µg/kg, respectively) were ~15 and ~4 times, respectively, higher than reference levels. Significant spatial and seasonal variations were observed for PAHs. Toxicity potentials of industrial and flood-plain soils were ~88 and ~8 times higher than reference levels. Trace metal concentrations in soils also showed marked dependencies on nearness to sources and seasonal effects. Correlation analysis, PAH diagnostic ratios and principal component analysis (PCA) led to the identification of sources such as coal and wood combustion, vehicular and industrial emissions, and atmospheric transport. Metal enrichment in soil and the degree of soil contamination were investigated using enrichment factors and index of geoaccumulation, respectively. Health risk assessment (incremental lifetime cancer risk and hazard index) showed that floodplain soils have potential high risk due to PAHs while industrial soils have potential risks due to both PAHs and Cr.

The role of nitroaromatic compounds (NACs) in constraining BrC absorption in the Indo-Gangetic Plain (IGP).

We present here the first measurements of nitroaromatic compounds (NACs) including nitrophenols (NPs), nitrocatechols (NCs) and nitrosalicylic acids (NSAs) from the Indian subcontinent and their role in constraining brown carbon (BrC) absorption. NACs at a rural receptor site in the eastern Indo-Gangetic Plain (IGP) (annual average: 185 ± 94 ng m-3) was dominated by NSAs (135 ± 77 ng m-3), followed by NPs (29 ± 11 ng m-3) and NCs (17 ± 16 ng m-3), with notable enrichments during nighttime and during the biomass burning seasons. An equilibrium absorption partitioning model estimated that >90 % of NSAs and NCs were in the particle-phase, suggesting lower degradation rates via oxidation and photolysis potentially due to year-round high relative humidity. While the contribution of NACs to organic aerosol mass was only 0.42 ± 0.23 %, their contribution to BrC absorption in the 300-450 nm range was higher by an order of magnitude (8 ± 4 %), with NCs and NSAs contributing almost equally in the low-visible (400-450 nm) range as at 365 nm. Despite having mass concentrations lower than NPs by factors of ∼2, contribution of NCs to BrC absorption at λ ≥ 400 nm was comparable to that by NPs, indicating the importance of the absorption efficiency of chromophores. The receptor model positive matrix factorization (PMF) quantified three major NAC sources: fossil fuel combustion (49 ± 15 %; annual average), secondary formation (40 ± 12 %), and biomass burning (11 ± 9 %), with variable contributions on seasonal and day-night bases. In summary, the study uncovered the significant role of NACs in constraining BrC absorption in the IGP, which stresses the importance for molecular-level characterization of BrC chromophores.

Compositional and optical characteristics of aqueous brown carbon and HULIS in the eastern Indo-Gangetic Plain using a coupled EEM PARAFAC, FT-IR and 1H NMR approach.

This study provides insights into the fluorophoric composition of aqueous brown carbon (BrCaq) and chemically-separated humic-like substances (HULIS): neutral HULIS (HULIS-n; at pH = 7) and acidic HULIS (HULIS-a; at pH = 2) on a seasonal and day-night basis in the eastern Indo-Gangetic Plain (IGP), India. A coupled approach including excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC) model, Fourier-transformed infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy was employed to understand the links between structural, compositional and fluorophoric characteristics of BrCaq and HULIS fractions. HULIS fluorophores (HULISfluoro) with varying oxidation states transported from the northwest IGP were dominant during biomass burning seasons (post-monsoon and winter), while protein-like fluorophores (PRLISfluoro) from marine emissions showed large contributions during summer. HULIS-n moieties were mostly primary in nature with higher conjugation, while HULIS-a were associated with secondarily formed and aged species with a larger contribution from degradation products. A substantial presence of tyrosine-like proteins in both chemically-separated HULIS fractions indicated that atmospheric HULIS is not entirely humic or fulvic-like in the eastern IGP. Finally, the dominance of H-C-O groups across seasons suggested consistent fossil fuel signatures along with season-specific influence of photodegradable cellulose from marine organisms in the summer and biomass burning in the post-monsoon and winter.

Size-distribution and driving factors of aerosol oxidative potential in rural kitchen microenvironments of northeastern India.

This study reports size-resolved dithiothreitol (DTT)-based oxidative potential (OP: total and water-soluble) in rural kitchens using liquefied petroleum gas (LPG), firewood (FW), and mixed biomass (MB) fuels in northeastern (NE) India. In comparison to LPG, volume-normalized total OP (OPtotal(v)DTT) was enhanced by a factor of ∼5 in biomass-using kitchens (74 ± 35 to 78 ± 42 nmol min-1 m-3); however, mass-normalized total OP (OPtotal(m)DTT) was similar between LPG and FW users and higher by a factor of 2 in MB-using kitchens. The water-insoluble OP (OPwi(v, m)DTT) fraction in OPtotal(v, m)DTT was greater than 50% across kitchens. Size distributions across kitchens and OPDTT categories ranged from unimodal to trimodal. OPws(v)DTT was driven by metals as well as organics across size fractions while OPwi(v)DTT was majorly constrained by metals with an increasing importance of organics in fine particles of biomass-using kitchens. Multiple linear regression analysis revealed that Cu and Ba explained 71% of the OPtotal(v)DTT variability in LPG-using kitchens, while water-soluble organic carbon (WSOC) and Ba were responsible for 44% variability in FW-using kitchens. Finally, the high internal dose of OPtotal(v)DTT (28-31 nmol min-1 m-3) in biomass-using kitchens established the severity of oxidative stress on the exposed population.

Profile of PAHs in the inhalable particulate fraction: source apportionment and associated health risks in a tropical megacity.

The present study proposed to investigate the atmospheric distribution, sources, and inhalation health risks of polycyclic aromatic hydrocarbons (PAHs) in a tropical megacity (Delhi, India). To this end, 16 US EPA priority PAHs were measured in the inhalable fraction of atmospheric particles (PM(10); aerodynamic diameter, ≤ 10 µm) collected weekly at three residential areas in Delhi from December 2008 to November 2009. Mean annual 24 h PM(10) levels at the sites (166.5-192.3 µg m(-3)) were eight to ten times the WHO limit. Weekday/weekend effects on PM(10) and associated PAHs were investigated. Σ(16)PAH concentrations (sum of 16 PAHs analyzed; overall annual mean, 105.3 ng m(-3); overall range, 10.5-511.9 ng m(-3)) observed were at least an order of magnitude greater than values reported from European and US cities. Spatial variations in PAHs were influenced by nearness to traffic and thermal power plants while seasonal variation trends showed highest concentrations in winter. Associations between Σ(16)PAHs and various meteorological parameters were investigated. The overall PAH profile was dominated by combustion-derived large-ring species (85-87 %) that were essentially local in origin. Carcinogenic PAHs contributed 58-62 % to Σ(16)PAH loads at the sites. Molecular diagnostic ratios were used for preliminary assessment of PAH sources. Principal component analysis coupled with multiple linear regression-identified vehicular emissions as the predominant source (62-83 %), followed by coal combustion (18-19 %), residential fuel use (19 %), and industrial emissions (16 %). Spatio-temporal variations and time-evolution of source contributions were studied. Inhalation cancer risk assessment showed that a maximum of 39,780 excess cancer cases might occur due to lifetime inhalation exposure to the analyzed PAH concentrations.

Disease burden and health risk to rural communities of northeastern India from indoor cooking-related exposure to parent, oxygenated and alkylated PAHs.

Exposure to a total of 51 targeted and non-targeted polycyclic aromatic hydrocarbons (PAHs) and their oxygenated and alkylated derivatives associated with size-segregated aerosol was investigated in rural kitchens using liquefied petroleum gas (LPG), mixed biomass (MB) and firewood (FW) fuels in northeastern India. The averaged PM10-associated parent-, alkylated-, and oxygenated-PAHs concentrations increased notably from LPG (257, 54, and 116 ng m-3) to MB (838, 119, and 272 ng m-3) to FW-using kitchens (2762, 225, and 554 ng m-3), respectively. PAHs were preferentially associated with the PM1 fraction with contributions increasing from 80 % in LPG to 86 % in MB and 90 % in FW-using kitchens, which in turn was dominated by <0.25 µm particles (54-75 % of the total). A clear profile of enrichment of low-molecular weight PAHs in cleaner fuels (LPG) and a contrasting enrichment of high-molecular weight PAHs in biomass-based fuels was noted. The averaged internal dose of Benzo[a]pyrene equivalent was the lowest in the case of LPG (19 ng m-3), followed by MB (161 ng m-3) and the highest in FW users (782 ng m-3). Estimation of incremental lifetime cancer risk (ILCR) from PAH exposure revealed extremely high cancer risk in biomass users (factors of 8-40) compared to LPG. The potential years of life lost (PYLL) and PYLL rate averaged across kitchen categories was higher for lung cancer (PYLL: 10.55 ± 1.04 years; PYLL rate: 204 ± 426) compared to upper respiratory tract cancer (PYLL: 10.02 ± 0.05 years; PYLL rate: 4 ± 7), and the PYLL rates for biomass users were higher by factors of 9-56 as compared to LPG users. These findings stress the need for accelerated governmental intervention to ensure a quick transition from traditional biomass-based fuels to cleaner alternatives for the rural population of northeastern India.

Understanding population exposure to size-segregated aerosol and associated trace elements during residential cooking in northeastern India: Implications for disease burden and health risk.

Mass-size distribution of respirable aerosol and 13 associated trace elements (TEs) were investigated in rural kitchens using liquefied petroleum gas (LPG), firewood and mixed biomass fuels across three northeastern Indian states. The averaged PM10 (particulate matter with aerodynamic diameter ≤ 10 µm) and ΣTE concentrations were 403 and 30 µg m-3 for LPG, 2429 and 55 µg m-3 for firewood, and 1024 and 44 µg m-3 for mixed biomass-using kitchens. Mass-size distributions were tri-modal with peaks in the ultrafine (0.05-0.08 µm), accumulation (0.20-1.05 µm), and coarse (3.20-4.57 µm) modes. Respiratory deposition, estimated using the multiple path particle dosimetry model, ranged from 21 % to 58 % of the total concentration across fuel types and population age categories. Head, followed by pulmonary and tracheobronchial, was the most vulnerable deposition region, and children were the most susceptible age group. Inhalation risk assessment of TEs revealed significant non-carcinogenic as well as carcinogenic risk, especially for biomass fuel users. The potential years of life lost (PYLL) was the highest for chronic obstructive pulmonary disease (COPD: 15.9 ± 3.8 years) followed by lung cancer (10.3 ± 0.3 years) and pneumonia (10.1 ± 0.1 years), while the PYLL rate was also highest for COPD, with Cr(VI) being the major contributor. Overall, these findings reveal the significant health burden faced by the northeastern Indian population from indoor cooking using solid biomass fuels.

Chitosan-Biotin-Conjugated pH-Responsive Ru(II) Glucose Nanogel: A Dual Pathway of Targeting Cancer Cells and Self-Drug Delivery.

The current study paves the way for improved chemotherapy by creating pH-responsive nanogels (NGs) (GC1 and GC2) loaded with synthetic ruthenium(II) arene complexes to increase biological potency. NGs are fabricated by the conjugation of chitosan (CTS)-biotin biopolymers that selectively target the cancer cells as CTS has the pH-responsive property, which helps in releasing the drug in cancer cells having pH ∼ 5.5, and biotin provides the way to target the cancer cells selectively due to the overexpression of integrin. The synthesized compounds and NGs were thoroughly characterized using various spectroscopic and analytical techniques such as NMR, electrospray ionization-mass spectrometry, Fourier transform infrared, UV-vis, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, rheology, Brunauer-Emmett-Teller, and others. NGs displayed exceptional increased efficacy toward cancerous cells with IC50 values ranging from 7.50 to 18.86 µM via induced apoptosis in three human cancer cell lines. Apart from its potency, NGs were found to be highly selective toward cancer cells. Moreover, based on the results of immunoblot analysis, it was observed that the synthesized compounds exhibit a significant increase in the expression of cleaved caspase-3 and a decrease in the expression of the antiapoptotic protein BCL-XL. Interestingly, the complexes were discovered to have the additional capability of catalyzing the conversion of NADH to NAD+, leading to the generation of radical oxygen species within the cells. Additionally, it was discovered that NG-induced apoptosis depends on ROS production and DNA binding. A narrower range of LD50 values (1185.93 and 823.03 µM) was seen after administering NGs to zebrafish embryos in vivo. The results support the use of drug-loaded NGs as potential chemotherapeutic and chemopreventive agents for human cancer cells.

Contribution of marine biological emissions to gaseous methylamines in the atmosphere: An emission inventory based on multi-source data sets.

Methylamines are a class of highly reactive organic alkaline gases in the atmosphere. At present, the gridded emission inventories of amines used in the atmospheric numerical model is mostly based on the amine/ammonia ratio method and do not consider the air-sea exchange of methylamines, which oversimplifies the emission scenario. Marine biological emissions (MBE), an important source of methylamines, has been insufficiently investigated. These shortcomings in the inventories can limit the simulation of amines by numerical models in the context of compound pollution in China. To acquire a more complete gridded inventory of amines (monomethylamine (MMA), dimethylamines (DMA), and trimethylamines (TMA)), we established a more reasonable MBE inventory of amines by using multi-source data sets (Sea Surface Temperature (SST), Chlorophyll-a (Chla), Sea Surface Salinity (SSS), NH3 column concentration (NH3), and Wind Speed (WS)), and merged it with the anthropogenic emissions (AE) inventory (by adopting the amine/ammonia ratio method and the Multi-resolution Emission Inventory for China (MEIC)). The new methodology can reveal the air-sea exchange fluxes and direction of different amines. Oceans can act as a sink for DMA and source for TMA while it can be either a source or sink for MMA. The concentration of amines above the coastal area increased significantly when the MBE was merged to the AE inventory. TMA and MMA showed significant increases, TMA increased by 43,917.0 %, and 804.0 %, in July 2015 and December 2019, respectively; while MMA increased by 2635.4 % and 0.37 % during the same periods; however, only slight changes were observed in the DMA concentration (-3.9 % in July 2015, and 1.1 % in December 2019). WS, Chla, and the total dissolved concentration of amines ([C+(s)tot]) were found to be the dominant factors affecting MBE fluxes. In addition, the emission fluxes and spatial distribution of AE, and wet deposition also affect the simulation of amines concentration.

Exploring a Redox-Active Ionic Porous Organic Polymer in Environmental Remediation and Electrochromic Application.

Here, we report the design and synthesis of a redox-active multifunctional ionic porous organic polymer iPOP-Bpy with exchangeable Br- ions, incorporating viologen as a redox-active building block. The material shows not only excellent iodine uptake capacity in the vapor phase (540 wt %) but also in the organic (1009.77 mg g-1) and aqueous phases (3921.47 mg g-1) with very fast adsorption kinetics in all cases. The material also shows its utility in being used as a solid-state NH3 vapor sensor as it shows very fast color switching in the presence of NH3 vapor. Furthermore, the material found application as a p-type complementary electrochromic electrode and was fabricated into a bilayer device. Excellent coloration efficiency, high switching speed, and good color contrast were obtained as investigated using bias-dependent optical and spectroelectrochemical studies, paving the way for fabricating power-efficient solid-state electrochromic devices.

Optical source apportionment of aqueous brown carbon (BrC) on a daytime and nighttime basis in the eastern Indo-Gangetic Plain (IGP) and insights from 13C and 15N isotopic signatures.

This study reports day-night and seasonal variations of aqueous brown carbon (BrCaq) and constituent humic-like substances (HULIS) (neutral and acidic HULIS: HULIS-n and HULIS-a) from the eastern Indo-Gangetic Plain (IGP) of India during 2019-2020. This is followed by the application of the receptor model positive matrix factorization (PMF) for optical source apportionment of BrCaq and the use of stable isotopic ratios (δ13C and δ15N) to understand atmospheric processing. Nighttime BrCaq absorption and mass absorption efficiencies (MAE) were enhanced by 40-150 % and 50-190 %, respectively, compared to the daytime across seasons, possibly as a combined effect from daytime photobleaching, dark-phase secondary formation, and increased nighttime emissions. MAE250 nm/MAE365 nm (i.e., E2/E3) ratios and Angstrom Exponents revealed that BrCaq and HULIS-n were relatively more aromatic and conjugated during the biomass burning-dominated periods while BrCaq and HULIS-a were comprised mostly of non-conjugated aliphatic structures from secondary processes during the photochemistry-dominated summer. The relative radiative forcing of BrCaq with respect to elemental carbon (EC) was 10-12 % in the post-monsoon and winter in the 300-400 nm range. Optical source apportionment using PMF revealed that BrCaq absorption at 300, 365 and 420 nm wavelengths in the eastern IGP is mostly from biomass burning (60-75 %), followed by combined marine and fossil fuel-derived sources (24-31 %), and secondary processes (up to 10 %). Source-specific MAEs at 365 nm were estimated to be the highest for the combined marine and fossil fuel source (1.34 m2 g-1) followed by biomass burning (0.78 m2 g-1) and secondary processing (0.13 m2 g-1). Finally, δ13C and δ15N isotopic analysis confirmed the importance of summertime photochemistry and wintertime NO3--dominated chemistry in constraining BrC characteristics. Overall, the quantitative apportionment of BrCaq sources and processing reported here can be expected to lead to targeted source-specific measurements and a better understanding of BrC climate forcing in the future.

Ruthenium(ii)-arene complexes as anti-metastatic agents, and related techniques.

With the discovery of cisplatin, a vast area of applications of metallodrugs in cancer treatment was opened but due to the side effects caused by the cisplatin complexes, researchers began to look for alternatives with similar anticancer properties but fewer side effects. Ruthenium was found to be a promising candidate, considering its significant anticancer properties and low side effects. Several ruthenium complexes, viz. NAMI-A, KP1019, KP1339, and TLD1433, have entered clinical trials. Some other arene ruthenium complexes such as RM175 and RAPTA-C have also entered clinical trials but very few of them have shown anti-metastatic properties. Herein, we provide information and probable mechanistic pathways for ruthenium(ii)-arene complexes that have been studied, so far, for their anti-metastatic activities. Also, we discuss the techniques and their significance for determining the anti-metastatic effects of the complexes.

Seven-year study of monsoonal rainwater chemistry over the mid-Brahmaputra plain, India: assessment of trends and source regions of soluble ions.

This work is a 7-year study of monsoonal rainwater chemistry (n = 302), over mid-Brahmaputra plain during 2012 to 2018. The samples were analyzed for major chemical parameters viz. pH, electrical conductivity (EC), and ions (SO42-, NO3-, Br-, Cl-, F-, Mg2+, Ca2+, K+, NH4+, Na+, and Li+) to assess the chemistry. The mean pH of rainwater varied among the years, which was maximum in 2018 (6.18 ± 0.72) and minimum in the year 2014 (5.39 ± 0.54), and the variations were significant at p < 0.0001. Ridgeline plots were drawn to visualize interannual variations, which revealed that Ca2+ was the dominant cation in the early years, whereas NH4+ prevailed in the latter years. Mann-Kendall analysis and Sen's slope statistical tests were employed, and it was found that all the ions showed positive S values indicating increasing trends. Enrichment factors (EF) of K+, SO42-, and NO3- were found to be high with respect to both soil and seawater suggesting the influence of emissions from fossil fuel and biomass burning in the chemistry of rainwater. Principal component analysis (PCA) was applied to identify the sources of rain constituents, and five factors were obtained explaining crustal dust, biomass burning, fossil fuel combustion, agricultural emissions, and coal burning as possible sources. Airmass back trajectory clusters and Potential Source Contribution Function (PSCF) were computed by application of HYbrid Single-Particle Lagrangian Integrated Trajectory model to appreciate the terrestrial influence on the chemistry. The results indicated inputs from both local and regional dust and anthropogenic constituents that influenced the monsoonal rainwater chemistry over Brahmaputra Valley.

Recognition and mechanistic investigation of anion sensing by ruthenium(II) arene complexes and bio-imaging application.

In this work, four new ruthenium complexes [Ru(η6-p-cymene)(L1)Cl] 1, [Ru(η6-p-cymene)(L2)Cl] 2, [Ru(η6-p-cymene)(L3)Cl] 3 and [Ru(η6-p-cymene)(L4)Cl] 4 [HL1 = (2-cyanophenyl)glycine; HL2 = (5-chloro-2-cyanophenyl)glycine; HL3 = (2-cyano-3-fluorophenyl)glycine; HL4 = (4-cyanophenyl)glycine] were synthesized and well characterized by several spectroscopic and analytical techniques. Complexes 1 and 3 were found to be fluorescent in most of the solvents; however, 2 and 4 were found to be fluorescent mostly in EtOAc, DMF and ethanol. Amongst these four complexes, 3 has shown selective sensing against CO32- and SO42- anions by quenching of fluorescence. The LOD values are found to be in the sub-micromolar range. Investigations of the sensing mechanism performed by computation and NMR studies indicate a possible adduct formation between the NH group of the ligand and the anion(s) through hydrogen bond formation, which ultimately might lead to proton transfer to the bi-negative anion. The quantum yield of the complex 3 was found to decrease on addition of CO32- and SO42- anions from 0.46 to 0.13 and 0.12, respectively. The Job's plot indicates the binding between the probe and anion in a 1 : 1 ratio for both CO32- and SO42- anions. Along with that, all the complexes were found to be biocompatible when tested against several cell lines showing very high IC50 values. It can also be observed that 1 is capable of penetrating within the cells and can act as a cell imaging agent showing fluorescence, and thus can be used for bio-imaging purposes.

Exploration of Alternative Approaches to Phenotyping of Late Leaf Spot and Groundnut Rosette Virus Disease for Groundnut Breeding.

Late leaf spot (LLS), caused by Nothopassalora personata (Berk. & M.A Curt.), and groundnut rosette disease (GRD), [caused by groundnut rosette virus (GRV)], represent the most important biotic constraints to groundnut production in Uganda. Application of visual scores in selection for disease resistance presents a challenge especially when breeding experiments are large because it is resource-intensive, subjective, and error-prone. High-throughput phenotyping (HTP) can alleviate these constraints. The objective of this study is to determine if HTP derived indices can replace visual scores in a groundnut breeding program in Uganda. Fifty genotypes were planted under rain-fed conditions at two locations, Nakabango (GRD hotspot) and NaSARRI (LLS hotspot). Three handheld sensors (RGB camera, GreenSeeker, and Thermal camera) were used to collect HTP data on the dates visual scores were taken. Pearson correlation was made between the indices and visual scores, and logistic models for predicting visual scores were developed. Normalized difference vegetation index (NDVI) (r = -0.89) and red-green-blue (RGB) color space indices CSI (r = 0.76), v* (r = -0.80), and b* (r = -0.75) were highly correlated with LLS visual scores. NDVI (r = -0.72), v* (r = -0.71), b* (r = -0.64), and GA (r = -0.67) were best related to the GRD visual symptoms. Heritability estimates indicated NDVI, green area (GA), greener area (GGA), a*, and hue angle having the highest heritability (H 2 > 0.75). Logistic models developed using these indices were 68% accurate for LLS and 45% accurate for GRD. The accuracy of the models improved to 91 and 84% when the nearest score method was used for LLS and GRD, respectively. Results presented in this study indicated that use of handheld remote sensing tools can improve screening for GRD and LLS resistance, and the best associated indices can be used for indirect selection for resistance and improve genetic gain in groundnut breeding.

Seasonal variations in aerosol acidity and its driving factors in the eastern Indo-Gangetic Plain: A quantitative analysis.

This study employs ISORROPIA-II for the evaluation of aerosol acidity and quantification of contributions from chemical species and meteorological parameters to acidity variation in the Indian context. PM2.5 samples collected during summer (April-July 2018), post-monsoon (September-November 2018), and winter (December 2018-January 2019) from a rural receptor location in the eastern Indo-Gangetic Plain (IGP) were analyzed for ionic species, water-soluble organic carbon (WSOC), and organic and elemental carbon (OC, EC) fractions. This was followed by estimation of the in situ aerosol pH and liquid water content (LWC) using the forward mode of ISORROPIA-II, which is less sensitive to measurement uncertainty compared to the reverse mode, for a K+-Ca2+-Mg2+-NH4+-Na+-SO42--NO3--Cl--H2O system. Aerosol pH was moderately acidic (summer: 2.93 ± 0.67; post-monsoon: 2.67 ± 0.23; winter: 3.15 ± 0.34) and was most sensitive to SO42- and total ammonium (TNH3) variation. The LWC of aerosol showed an increasing trend from summer (16.6 ± 13.6 µg m-3) through winter (32.9 ± 10.4 µg m-3). With summer as the baseline, the largest changes in aerosol pH during the other seasons was driven by SO42- (ΔpH: -0.70 to -0.82 units), followed by TNH3 (ΔpH: +0.25 to +0.38 units) with K+ and temperature being significant only during winter (ΔpH: +0.51 and + 0.46 units, respectively). The prevalent acidity regime provided three major insights: i) positive summertime Cl- depletion (49 ± 20%) as a consequence of SO42- substitution increased aerosol pH by 0.03 ± 0.20 units and decreased LWC by 2.4 ± 5.9 µg m-3; ii) the rate of strong acidity (H+str) neutralization and the [H+str]/[SO42-] molar ratio suggested the existence of bounded acidity in ammonium-rich (winter) conditions; and iii) significant correlations between LWC, WSOC, and secondary organics during post-monsoon and winter pointed towards a possible indirect role of WSOC in enhancing LWC of aerosol, thereby increasing pH. Given the inability of proxies such as H+str and charge ratios to accurately represent aerosol pH as demonstrated here, this study emphasizes the need for rigorous thermodynamic model-based evaluation of aerosol acidity in the Indian scenario.

Are fireworks a significant episodic source of brown carbon?

We hypothesize that firework events involving the combustion of charcoal fuel, organic binders, metal salts, and cellulose-based wrapping material could be significant transient sources of aerosol brown carbon (BrC). To test this, we couple high time-resolution (1 min) measurements of black carbon (BC) and BrC absorption from a 7-wavelength aethalometer with time-integrated (12-24 h) measurements of filter extracts, i.e., UV-visible, fluorescence, and Fourier-transformed infrared (FT-IR) signatures of BrC, total and water-soluble organic carbon (OC and WSOC), ionic species, and firework tracer metals during a sampling campaign covering the Diwali fireworks episode in India. In sharp contrast to BC, BrC absorption shows a distinct and considerable rise of 2-4 times during the Diwali period, especially during the hours of peak firework activity, as compared to the background. Fluorescence profiles suggest enrichment of humic-like substances (HULIS) in the firework plume, while the enhancement of BrC absorption in the 400-500 nm range suggests the presence of nitroaromatic compounds (NACs). Considerable contributions of WSOC and secondary organics to OC (44.1% and 31.2%, respectively) and of the water-soluble fraction of BrC to total BrC absorption (71.0%) during the Diwali period point toward an atmospherically processed, polar signature of firework-related BrC, which is further confirmed by FT-IR profiles. This aqueous BrC exerts a short-lived but strong effect on atmospheric forcing (12.0% vis-à-vis BC in the UV spectrum), which could affect tropospheric chemistry via UV attenuation and lead to a stabilization of the post-Diwali atmosphere, resulting in enhanced pollutant build-up and exposure.

Peanut Leaf Wilting Estimation From RGB Color Indices and Logistic Models.

Peanut (Arachis hypogaea L.) is an important crop for United States agriculture and worldwide. Low soil moisture is a major constraint for production in all peanut growing regions with negative effects on yield quantity and quality. Leaf wilting is a visual symptom of low moisture stress used in breeding to improve stress tolerance, but visual rating is slow when thousands of breeding lines are evaluated and can be subject to personnel scoring bias. Photogrammetry might be used instead. The objective of this article is to determine if color space indices derived from red-green-blue (RGB) images can accurately estimate leaf wilting for breeding selection and irrigation triggering in peanut production. RGB images were collected with a digital camera proximally and aerially by a unmanned aerial vehicle during 2018 and 2019. Visual rating was performed on the same days as image collection. Vegetation indices were intensity, hue, saturation, lightness, a∗, b∗, u∗, v∗, green area (GA), greener area (GGA), and crop senescence index (CSI). In particular, hue, a∗, u∗, GA, GGA, and CSI were significantly (p ≤ 0.0001) associated with leaf wilting. These indices were further used to train an ordinal logistic regression model for wilting estimation. This model had 90% accuracy when images were taken aerially and 99% when images were taken proximally. This article reports on a simple yet key aspect of peanut screening for tolerance to low soil moisture stress and uses novel, fast, cost-effective, and accurate RGB-derived models to estimate leaf wilting.

Corrigendum: Peanut Leaf Wilting Estimation From RGB Color Indices and Logistic Models.

[This corrects the article DOI: 10.3389/fpls.2021.658621.].