Identifying Quinones in Complex Aqueous Environmental Media (Biochar Extracts) through Tagging with Cysteine and Cysteine-Contained Peptides and High Resolution Mass Spectrometry Analysis.

Quinones are among the most important components in natural organic matter (NOM) for redox reactions; however, no quinones in complex environmental media have been identified. To aid the identification of quinone-containing molecules in ultracomplex environmental samples, we developed a chemical tagging method that makes use of a Michael addition reaction between quinones and thiols (-SH) in cysteine (Cys) and cysteine-contained peptides (CCP). After the tagging, candidates of quinones in representative aqueous environmental samples (water extractions of biochar) were identified through high-resolution mass spectrometry (HRMS) analysis. The MS and UV spectra analysis showed rapid reactions between Cys/CCP and model quinones with ß-carbon from the same benzene ring available for Michael addition. The tagging efficiency was not influenced by other co-occurring nonquinone representative compounds, including caffeic acid, cinnamic acid, and coumaric acid. Cys and CCP were used to tag quinones in water extractions of biochars, and possible candidates of quinones (20 and 53 based on tagging with Cys and CCP, respectively) were identified based on the HRMS features for products of reactions with Cys/CCP. This study has successfully demonstrated that such a Michael addition reaction can be used to tag quinones in complex environmental media and potentially determine their identities. The method will enable an in-depth understanding of the redox chemistry of NOM and its critical chemical compositions and structures.

High-Resolution Tandem Mass Spectrometry-Based Analysis of Model Lignin-Iron Complexes: Novel Pipeline and Complex Structures.

Understanding the chemical nature of soil organic carbon (SOC) with great potential to bind iron (Fe) minerals is critical for predicting the stability of SOC. Organic ligands of Fe are among the top candidates for SOCs able to strongly sorb on Fe minerals, but most of them are still molecularly uncharacterized. To shed insights into the chemical nature of organic ligands in soil and their fate, this study developed a protocol for identifying organic ligands using ultrahigh-performance liquid chromatography-high-resolution tandem mass spectrometry (UHPLC-HRMS/MS) and metabolomic tools. The protocol was used for investigating the Fe complexes formed by model compounds of lignin-derived organic ligands, namely, caffeic acid (CA), p-coumaric acid (CMA), vanillin (VNL), and cinnamic acid (CNA). Isotopologue analysis of 54/56Fe was used to screen out the potential UHPLC-HRMS (m/z) features for complexes formed between organic ligands and Fe, with multiple features captured for CA, CMA, VNL, and CNA when 35/37Cl isotopologue analysis was used as supplementary evidence for the complexes with Cl. MS/MS spectra, fragment analysis, and structure prediction with SIRIUS were used to annotate the structures of mono/bidentate mono/biligand complexes. The analysis determined the structures of monodentate and bidentate complexes of FeLxCly (L: organic ligand, x = 1-4, y = 0-3) formed by model compounds. The protocol developed in this study can be used to identify unknown organic ligands occurring in complex environmental samples and shed light on the molecular-level processes governing the stability of the SOC.

A mini review on 6PPD quinone: A new threat to aquaculture and fisheries.

Numerous toxic substances are directly and indirectly discharged by humans into water bodies, causing distress to the organisms living on it. 6PPD, an amino antioxidant from tires reacts with ozone to form 6PPD-Q, which has garnered global attention due to its lethal nature to various organisms. This review aims to provide an understanding of the sources, transformation, and fate of 6PPD-Q in water and the current knowledge on its effects on aquatic organisms. Furthermore, we discuss research gaps pertaining to the mechanisms by which 6PPD-Q acts within fish bodies. Previous studies have demonstrated the ubiquitous presence of 6PPD-Q in the environment, including air, water, and soil. Moreover, this compound has shown high lethality to certain fish species while not affecting others. Toxicological studies have revealed its impact on the nervous system, intestinal barrier function, cardiac function, equilibrium loss, and oxidative stress in various fish species. Additionally, exposure to 6PPD-Q has led to organ injury, lipid accumulation, and cytokine production in C. elegans and mice. Despite studies elucidating the lethal dose and effects of 6PPD-Q in fish species, the underlying mechanisms behind these symptoms remain unclear. Future studies should prioritize investigating the mechanisms underlying the lethality of 6PPD-Q in fish species to gain a better understanding of its potential effects on different organisms.

Quantification of Quinones in Environmental Media by Chemical Tagging with Cysteine-Containing Peptides Coupled to Size Exclusionary Separation.

Quinones are one of the most important redox-reactive organic compounds in natural environments, such as soil, water, and sediment, playing an important role in regulating the environmental processes and biogeochemical cycles of critical elements under climate change, including the influences of extreme events such as wildfires. However, to date, no existing methods can quantify quinones in complex environmental media. To overcome this challenge, a quantification method was developed by coupling chemical tagging of quinones by cysteine-containing nonaromatic peptides (Cpep) through a Michael addition reaction with size exclusionary chromatography (SEC) separation and ultraviolet (UV) analysis─leveraging on the characteristic absorbance of aromatic rings at 254 nm and molecular size of peptide. The method was demonstrated using model quinones, including 1,4-benzoquinone (BQ), 1,4-naphthoquinone (NQ), and 1,4-anthraquinone (AQ), with a detection limit of 3.3, 0.7, and 0.2 µM, respectively. Concentrations of quinones in water extractions of biochars, soils, and wildfire-derived ashes were determined to range from 0.8 to 14 µM and were positively correlated with their redox reactivity determined by a chemical assay. This method provides a novel rapid quantification of quinones in complex environmental media as well as a quick assessment for redox reactivity and opens up new avenues for studying environmental transformation and remediation of contaminants.

Foliar application of green synthesized ZnO nanoparticles reduced Cd content in shoot of lettuce.

Though Zinc (Zn) supplementation can mitigate root-based Cadmium (Cd) uptake in plants, the impact of foliar-applied Zinc Oxide nanoparticles (ZnO NPs) on this process remains under-explored. This study investigates the influence of foliar-applied ZnO NPs on the growth of lettuce and its Cd uptake in Cd-contaminated soil in greenhouse setting. Green synthesized ZnO (G-ZnO) NPs (10 and 100 mg/L) using sweet potato leaf extracts were used, and compared with commercially available ZnO (C-ZnO) NPs (100 mg/L) for their efficacy. Scanning electron microscopy and Fourier-transform infrared spectroscopy were used for G-ZnO NPs characterization. Shoot dry weight, antioxidant activity, and chlorophyll content were all negatively affected by Cd but positively affected by ZnO NPs application. ZnO NPs application resulted in a notable reduction in lettuce Cd uptake, with the highest reduction (43%) observed at 100 mg/L G-ZnO NPs. In the lettuce shoot, Zn and Cd concentration showed a significant inverse correlation (R2 = 0.79-0.9, P < 0.05). This study offers insights into the impact of chemical and green synthesized ZnO NPs on enhancing crop growth under stress conditions, and their role in modulating Cd uptake in plants, indicating potential implications for sustainable agricultural practices.

Effects of microplastics and nanoplastics in shrimp: Mechanisms of plastic particle and contaminant distribution and subsequent effects after uptake.

To date, previous studies have reported the adverse effects of microplastics (MPs) and nanoplastics (NPs) on both freshwater and marine organisms. However, the information on MPs' and NPs' effects on shrimp species is scarce. In addition, the factors influencing the distribution of these particles in aquatic systems have been explained, yet the mechanisms behind MPs and NPs distribution and consumption, specifically to crustaceans and shrimp, have not been elucidated in detail. The effects of MPs and NPs as well as plastic-carried contaminants and pathogens on shrimp are critical to shrimp production and subsequent human consumption. Recent findings are required to review and discuss to open up new avenues for emerging Shrimp and crustacean research for sustainability. This review summarizes the distribution and fate of MPs and NPs along with contaminants and pathogens and identifies potential risks to shrimp health. The transport of MPs and NPs is influenced by their plastic properties, hydrodynamics, and water properties. Additionally, the fate of these particles on a plastic surface (plastisphere) is regulated by contaminant properties. Pathogens thriving on plastic surfaces and contaminants adsorbed can reach aquatic organisms directly with plastic particles or indirectly after release to an aquatic environment. MPs and NPs can be absorbed by shrimp through their gills and mouth and accumulate in their internal organs. Innate immunity influenced the degree of survival rate, tissue damage, alteration of gut microbiota, and increased oxidative stress caused by MPs and NPs accumulation. The studies on the effects of MPs and NPs are still not sufficient to understand how these particles are absorbed from various parts of the shrimp body and the fate of these plastics inside the body.

Ascent rate and the Lake Louise scoring system: An analysis of one year of emergency ward entries for high-altitude sickness at the Mustang district hospital, Nepal.

More travellers are making swift ascents to higher altitudes without sufficient acclimatization or pharmaceutical prophylaxis as road connectivity develops in the Himalayan region of Nepal. Our study connects ascent rate with prevalence and severity of acute mountain sickness (AMS) among patients admitted to the emergency ward of the Mustang district hospital in Nepal. A register-based, cross-sectional study was conducted between June 2018 and June 2019 to explore associations of Lake Louise scores with ascent profile, sociodemographic characteristics, and comorbidities using chi-square test, t-test, and Bayesian logistic regression. Of 105 patients, incidence of AMS was 74%, of which 61%, 36%, and 3% were mild, moderate, and severe cases, respectively. In the Bayesian-ordered logistic model of AMS severity, ascent rate (odds ratio 3.13) and smoking (odds ratio 0.16) were significant at a 99% credible interval. Based on the model-derived counterfactual, the risk of developing moderate or severe AMS for a middle-aged, non-smoking male traveling from Pokhara to Muktinath (2978m altitude gain) in a single day is twice that of making the ascent in three days. Ascent rate was strongly associated with the likelihood of developing severe AMS among travellers with AMS symptoms visiting Mustang Hospital's Emergency Ward.