Development, validation and a GAPI greenness assessment for the determination of 103 pesticides in mango fruit drink using LC-MS/MS.

A robust method was developed using LC-ESI-MS/MS-based identification and quantification of 103 fortified pesticides in a mango fruit drink. Variations in QuEChERS extraction (without buffer, citrate, and/or acetate buffered) coupled with dispersive clean-up combinations were evaluated. Results showed 5 mL dilution and citrate buffered QuEChERS extraction with anhydrous (anhy) MgSO4 clean-up gave acceptable recovery for 100 pesticides @ 1 µg mL-1 fortification. The method was validated as per SANTE guidelines (SANTE/11813/2021). 95, 91, and 77 pesticides were satisfactorily recovered at 0.1, 0.05, and 0.01 µg mL-1 fortification with HorRat values ranging from 0.2-0.8 for the majority. The method showed matrix enhancement for 77 pesticides with a global uncertainty of 4.72%-23.89%. The reliability of the method was confirmed by real sample analysis of different brands of mango drinks available in the market. The greenness assessment by GAPI (Green Analytical Procedure Index) indicated the method was much greener than other contemporary methods.

Molecular distribution, sources and potential health risks of fine particulate-bound polycyclic aromatic hydrocarbons during high pollution episodes in a subtropical urban city.

Abundance of fine particulate-bound 16 priority polycyclic aromatic hydrocarbons (PAHs) was investigated to ascertain its sources and potential carcinogenic health risks in Varanasi, India. The city represents a typical urban settlement of South Asia having particulate exposure manyfold higher than standard with reports of pollution induced mortalities and morbidities. Fine particulates (PM2.5) were monitored from October 2019 to May 2020, with 32% of monitoring days accounting ≥100 µgm-3 of PM2.5 concentration, frequently from November to January (99% of monitoring days). The concentration of 16 priority PAHs varied from 24.1 to 44.6 ngm-3 (mean: 33.1 ± 3.2 ngm-3) without much seasonal deviations. Both low (LMW, 56%) and high molecular weight (HMW, 44%) PAHs were abundant, with Fluoranthene (3.9 ± 0.4ngm-3) and Fluorene (3.5 ± 0.3ngm-3) emerged as most dominating PAHs. Concentration of Benzo(a)pyrene (B(a)P, 0.5 ± 0.1ngm-3) was lower than the national standard as it contributed 13% of total PAHs mass. Diagnostic ratios of PAH isomers indicate predominance of pyrogenic sources including emissions from biomass burning, and both from diesel and petrol-driven vehicles. Source apportionment using receptor model revealed similar observation of major PAHs contribution from biomass burning and fuel combustion (54% of source contribution) followed by coal combustion for residential heating and cooking purposes (44%). Potential toxicity of B[a]P equivalence ranged from 0.003 to 1.365 with cumulative toxicity of 2.13ngm-3. Among the PAH species, dibenzo[h]anthracene contributed maximum toxicity followed by B[a]P, together accounting 86% of PAH induced carcinogenicity. Incremental risk of developing cancer through lifetime exposure (ILCR) of PAHs was higher in children (3.3 × 10-4) with 56% contribution from LMW PAHs, primarily through ingestion and dermal contact. Adults in contrast, were more exposed to inhale airborne PAHs with cumulative ILCR of 2.2 × 10-4. However, ILCR to PM2.5 exposure is probably underestimated considering unaccounted metal abundance thus, require source-specific control measures.

Palladium encapsulated nanofibres for scavenging ethylene from sapota fruits.

Scavenging ethylene is a useful intervention during the transportation and storage of tropical climacteric fruits like sapota. Sapota (Manilkara achras Mill.) is a delicious tropical fruit with a very high respiration rate and poor shelf life. To prolong its post-harvest shelf life, the use of palladium chloride in electrospun nanomats was evaluated at a concentration varying from 1 to 4% levels. Encapsulation of 1-2% PdCl2 in nanomats increased the ethylene scavenging capacity (ESC) by 47-68%. Although, upon encapsulation, both PdCl2 and potassium permanganate showed significantly the same ethylene scavenging activity, the efficacy of PdCl2 was found better in presence of sapota fruits. The PdCl2 nanomats were brighter (L* > 73) in colour compared to the potassium permanganate mat. The placement of nanomats (2 cm2 × 9 cm2) in corrugated fibre board boxes in which the sapota was packed showed higher quality indices (firmness, TSS, ascorbic acid, and phenolics) along with lower PLW and respiration rate during the 8 days of storage period. Compared to control (8.35%), physiological loss in weight of 4.47% was recorded in fruits stored with ethylene scavenging nanomats. PdCl2 encapsulated PVA nanomats can emerge as a promising option for the retention of quality in fruits during storage and transit.

Evidences of microplastics in aerosols and street dust: a case study of Varanasi City, India.

Microplastics (MPs) are ubiquitous in our environment. Its presence in air, water, and soil makes it a serious threat to living organisms and has become a critical challenge across ecosystems. Present study aimed to assess the abundance of MPs in aerosols and street dust in Varanasi, a typical urban city in Northern India. Airborne particulates and street dust samples were collected from various sampling sites around Varanasi City. The physical identification of MPs was conducted by binocular microscopy, fluorescence microscopy, and scanning electron microscopy (SEM), while elemental analysis was made by energy-dispersive X-ray (EDX). Finally, Fourier-transform infrared spectroscopy (FTIR) was used for chemical characterization of MPs. Presence of MPs in both aerosols and street dust from all selected sampling sites was confirmed, however with varying magnitude. MPs of different colors having the shape of fragments, films, spherules, and fibers were recorded in the study while fragments (42%) in street dust and fibers (44%) dominated in aerosols. Majority of the MPs were < 1 mm in size and were primarily polypropylene, polystyrene, polyethylene, polyethylene terephthalate, polyester, and polyvinyl chloride types. The EDX spectra showed the presence of toxic inorganic contaminants like metallic elements on MPs, especially elements like aluminum, cadmium, magnesium, sodium, and silicon found to adsorb on the MPs. Presence of MPs in the airborne particulates and street dust in Varanasi is reported for the first time, thus initiating further research and call for a source-specific management plan to reduce its impact on human health and environment.

Development of a QuEChERS-LCMS/MS method for simultaneous estimation of tebuconazole and chlormequat chloride in wheat crop.

Tebuconazole (TBZ) and Chlormequat chloride (CCC) combination has been established as highly effective in reducing plant height of lodging prone wheat varieties. In this work, a novel analytical method employing the quick, easy, cheap, effective, rugged and safe (QuEChERS) cleanup technique and LC-MS/MS (liquid chromatography-tandem mass spectroscopy) was developed for simultaneous estimation of TBZ and CCC in wheat grains and harvest stage plant leaves. A total of 10 mL of acetonitrile and 50 mg of primary secondary amine (PSA) sorbent was consumed in the optimized QuEChERS process for leaves and grain samples. The LC-MS/MS analysis was performed using a C-18 column operating under electrospray ionization in positive mode. The QuEChERS approach achieved extraction recoveries in the acceptable range of 70%-120%, for both the compounds and was validated in terms of accuracy, precision, sensitivity and linearity. Persistence study was conducted using Lihocin (CCC 50% SL), Folicur (TBZ 25.9% EC) and their combination tank mix (Lihocin + Folicur-50% SL + 25.9% EC) applied as foliar spray twice in wheat crop (tester tall variety C-306). The results demonstrated that the developed QuEChERS-LCMS/MS is rapid and confirmatory for simultaneous quantification of both the test analytes in wheat crop.

Source apportionment and health risk assessment of airborne particulates over central Indo-Gangetic Plain.

Sources of airborne particulates (PM10) were investigated in two contrasting sites over central Indo-Gangetic Plain (IGP), one representing a rural background (Mirzapur) and another as an urban pollution hotspot (Varanasi). Very high PM10 concentration was noted both in Varanasi (178 ± 105 µgm-3; N:435) and Mirzapur (131 ± 56 µgm-3; N:169) with 72% and 62% of monitoring days exceeded the national air quality standard, respectively. Particulate-bound elements contribute significant proportion of PM10 mass (15%-18%), with highest contribution from Ca (7%-10%) and Fe (2%-3%). Besides, presence of Zn (1%-3%), K (1%-2%) and Na (1%-2%) was also noted. Water-soluble ionic species contributed 15%-19% of particulate mass, primarily by the secondary inorganic aerosols (SIA). Among the SIA, sulphate (5%-7%) and nitrate (4%) were prominent, contributing 59%-62% of the total ionic load, especially in winter. Particulate-bound metallic species and ions were selectively used as signatory molecules and source apportionment of PM10 was done by multivariate factor analysis. UNMIX was able to extract particulate sources in both the locations and crustal resuspensions (dust/-soil) were identified as the dominant source contributing 57%-63% of PM10 mass. Secondary aerosols were the second important source (17%-23%), followed by emissions from biomass/-refuse burning (10-19%). Transport of airborne particulates from upper IGP by prevailing westerly were identified as the important contributor of particulates, especially during high particulate loading days. Health risks associated to particulate-bound toxic metal exposure were also assessed. Non-carcinogenic health risk was within the permissible limit while there is possibility of elevated risk for PM10-bound Cr and Cd, if adequate control measures are not in place.

Temporal evolution of submicron particles during extreme fireworks.

Evolution of submicron particles in terms of particle number concentration and mobility-equivalent diameter was measured during Diwali festival-specific intensive pyrotechnic displays in Varanasi over central Indo-Gangetic Plain (IGP). A scanning mobility particle sizer coupled with an optical particle sizer was used to fit in an overlapping size range, and particle number concentration was analyzed to have an insight into the new particle formation and subsequent evolution of particles from nucleation to accumulation mode. Further, variation in black carbon (BC) concentration and aerosol ionic composition was measured simultaneously. Frequent fluctuation in particle number concentration in and around Diwali festival was evidenced, primarily influenced by local emission sources and meteorology, with three distinct peaks in number concentrations (dN/dlogDp, 3.1-4.5 × 104 cm3) coinciding well with peak firework emission period (18:00-23:00 h). Submicron particle size distribution revealed a single peak covering a size range of 80-130 nm, and for all instances, number concentration maximum coincided with geometric mean minimum, indicating the emission primarily in the ultrafine range (< 0.1 µm). Interestingly, during peak firework emissions, besides rise in accumulation mode, an event of new particle formation was identified with increase in nucleation and small Aitken mode, before being dispersed to background aerosols. On an integral scale, a clear distinction was noted between a normal and an episodic event, with a definite shift in the formation of ultrafine particles compared with the accumulation mode. The BC diurnal profile was typical, with a prominent nocturnal peak (12.0 ± 3.9 µg m-3) corresponding to a decrease in the boundary layer height. A slight variation in maximum BC concentration (16.8 µg m-3) was noted in the night of the event coinciding well with firework emissions. An increase in some specific ionic species was also noted in combination with an increase in the overall cation to anion ratio, which was explained in terms of heterogeneous transformation of NOx and catalytic conversion of SO2. Graphical abstract Time-resolved evolution of particle size distribution during normal and episodic events.