Insight into the sorption and desorption pattern of pyrrolizidine alkaloids and their N-oxides in acidic tea (Camellia sinensis) plantation soils.

Pyrrolizidine alkaloids (PAs) and their N-oxides (PANOs) are phytotoxins produced by various plant species and have been emerged as environmental pollutants. The sorption/desorption behaviors of PAs/PANOs in soil are crucial due to the horizontal transfer of these natural products from PA-producing plants to soil and subsequently absorbed by plant roots. This study firstly investigated the sorption/desorption behaviors of PAs/PANOs in tea plantation soils with distinct characteristics. Sorption amounts for seneciphylline (Sp) and seneciphylline-N-oxide (SpNO) in three acidic soils ranged from 2.9 to 5.9 µg/g and 1.7 to 2.8 µg/g, respectively. Desorption percentages for Sp and SpNO were from 22.2% to 30.5% and 36.1% to 43.9%. In the mixed PAs/PANOs systems, stronger sorption of PAs over PANOs was occurred in tested soils. Additionally, the Freundlich models more precisely described the sorption/desorption isotherms. Cation exchange capacity, sand content and total nitrogen were identified as major influencing factors by linear regression models. Overall, the soils exhibiting higher sorption capacities for compounds with greater hydrophobicity. PANOs were more likely to migrate within soils and be absorbed by tea plants. It contributes to the understanding of environmental fate of PAs/PANOs in tea plantations and provides basic data and clues for the development of PAs/PANOs reduction technology.

Continuous atmospheric pressure interfaced ion trap mass spectrometry with thermal desorption for detection of nonvolatile drugs.

The escalating need for prompt and highly sensitive on-site detection of trace-level drugs is fueling the advancement of miniature, high-performance mass spectrometers and analytical methodologies. In this study, a miniature continuous atmospheric pressure interfaced ion trap mass spectrometer integrated with thermal desorption acetone-assisted photoionization (TD-CAPI-ITMS) was developed for highly sensitive detection of nonvolatile drugs in saliva and blood. By strategically extending the sampling time of the TD-CAPI-ITMS to cover the entire desorption process, a remarkable two-order-of-magnitude enhancement in the signal intensity of individual drugs was observed. Moreover, the simultaneous detection of drug mixtures with widely varying boiling points and saturation vapor pressures was accomplished. Optimization of the parameters yielded a limit of detection (LOD) for ketamine and 5F-EMB-PICA of 1 pg/µL accompanied by a robust stability, as evidenced by a relative standard deviation (RSD) of 5.30 %. Combined with straightforward liquid-liquid extraction, the sensitivity of drugs in saliva as low as 10 pg/µL was achieved, which met the requirements of Chinese national standard GA1333-2017. Owing to its exceptional sensitivity, the matrix effect present in blood samples was significantly alleviated through dilution, allowing for accurate monitoring of antibiotic concentrations. The results underscore the substantial potential of the TD-CAPI-ITMS for lab-free applications in drug-related forensic analysis, therapeutic drug monitoring, and pharmacokinetic studies.

Feasibility of qualitative identification of some metal elements in rice grains using laser desorption ionization-time of flight mass spectrometry.

Rice is one of the popular foods in the world, and the identification and measurement of the concentration of metal elements in therein is necessary for food safety. To this end, this work investigated the feasibility of using laser desorption ionization time-of-flight mass spectrometry (LDI-TOF-MS) for the qualitative identification of metal elements present in rice. The effect of different sample preparation methods (solvation of rice powder in water, acid digestion, and rice tablet) and laser wavelength on the mass spectral pattern of rice was investigated. Based on the experimental results, LDI-TOF-MS proves to be a reliable method for the qualitative identification of the metal elements in rice. It was determined that the rice sample prepared as a tablet and using visible laser radiation, are the most suitable choice for the identification of metallic elements using LDI-TOF-MS. The mass spectrum of rice was experimentally modeled using starch and theoretically simulated.

Spatial metabolomics to discover hypertrophic scar relevant metabolic alterations and potential therapeutic strategies: A preliminary study.

Spatially mapping the metabolic remodeling of hypertrophic scar and surrounding normal skin tissues has the potential to enhance our comprehension of scar formation and aid in the advancement of therapeutic interventions. In this study, we employed matrix-assisted laser desorption/ionization (MALDI), a mass spectrometry imaging technique, to visualize the hierarchical distribution of metabolites within sections of hypertrophic scar and surrounding normal skin tissues. A comprehensive analysis identified a total of 1631 metabolites in these tissues. The top four classes that were identified included benzene and substituted derivatives, heterocyclic compounds, amino acids and its metabolites, and glycerophospholipids. In hypertrophic scar tissues, 22 metabolites were upregulated and 66 metabolites were downregulated. MetaboAnalyst pathway analysis indicated that glycerophospholipid metabolism was primarily associated with these altered 88 metabolites. Subsequently, six metabolites were selected, their spatial characteristics were analyzed, and they were individually added to the cell culture medium of primary hypertrophic scar fibroblasts. The preliminary findings of this study demonstrate that specific concentrations of 1-pyrrolidinecarboxamide, 2-benzylideneheptanal, glycerol trioleate, Lyso-PAF C-16, and moxonidine effectively inhibited the expressions of COL1A1, COL1A2, COL3A1, and ACTA2. These bioactive metabolites exhibit mild and non-toxic properties, along with favorable pharmacokinetics and pharmacodynamics, making them promising candidates for drug development. Consequently, this research offers novel therapeutic insights for hypertrophic scar treatment.

Collision cross sections of large positive fullerene molecular ions and their use as ion mobility calibrants in trapped ion mobility mass spectrometry.

Positive-ion laser desorption/ionization (LDI) of fullerenes contained in soot as produced by the Krätschmer-Huffman process delivers a wide range of fullerene molecular ions from C56+• to above C300+•. Here, the collision cross section (CCS) values of those fullerene molecular ions are determined using a trapped ion mobility-quadrupole-time-of-flight (TIMS-Q-TOF) instrument. While CCS values in the range from C60+• to C96+• are already known with high accuracy, those of ions from C98+• onward had yet to be determined. The fullerene molecular ions covered in this work have CCS values from about 200 to 440 Å2. The fullerene molecular ion series is evenly spaced at C2 differences in composition, and thus, small CCS differences of just 2.2-3.5 Å2 were determined across the entire range. Fullerene M+• ions may be employed as mobility calibrants, in particular, when very narrow 1/K0 ranges are being analyzed to achieve high TIMS resolving power. In addition, due to the simple elemental composition, M+• ions of fullerenes could also serve for mass calibration. This study describes the determination of CCS values of fullerene molecular ions from C56+• to C240+• and the application of ions from C56+• to C220+• to calibrate the ion mobility scale of a Bruker timsTOFflex instrument in any combination of LDI, matrix-assisted laser desorption/ionization (MALDI), and electrospray ionization (ESI) modes in the CCS range from about 200 to 420 Å2. This use was exemplified along with ions from Agilent Tune Mix, leucine-enkephalin, angiotensin I, angiotensin II, and substance P.

Enhanced Hydrophilicity of DAAQ-TFP COFs via Sulfonate Modification for Air Water Harvesting in Arid Environment.

The poor ability of covalent organic frameworks (COFs) based adsorbents at low relative humidity (RH) conditions limits their applications for air-water harvesting in arid environments. In the present work, the sulfonated COFs (DAAQ-TFP-SO3H@LiCl) composites are prepared through the functionalization of sulfonic acid and LiCl composite to improve its hydrophilicity. TheDAAQ-TFP-SO3H@LiCl composites exhibit a good adsorption performance, outperforming many other COF adsorbents developed so far. It can absorb 0.22 ± 0.005 g g-1 and 1.01 ± 0.027 g g-1 of water at room temperature under 20% RH and 90% RH, respectively while demonstrating good cyclic stability. Compared with the isotherm of the DAAQ-TFP, the introduction of the sulfonic acid group shifts the inflection point of the water isotherm toward low humidity, indicating that the sulfonic acid group effectively expends the working humidity range of the adsorbent and enables the effective water adsorption in an arid environment. Furthermore, the DAAQ-TFP-SO3H@LiCl composites display rapid kinetics during both the adsorption and desorption processes, reaching saturation within 60 min in the equilibrium adsorption test and completing desorption within 12 min at 50 °C. This innovative approach provides a new method for designing adsorbent materials with low energy input requirements and high daily water consumption capabilities.

Regulating the 3d-orbital occupancy on Ni sites enables high-rate and durable Ni(OH)2 cathode for alkaline Zn batteries.

The capacity and cycling stability of ß-Ni(OH)2-based cathodes in aqueous alkaline Ni-Zn batteries are still unsatisfactory due to their undesirable OH- adsorption/desorption dynamics during the electrochemical redox process. To settle this issue, we introduce a new atomic-level strategy to finely modulate the OH- adsorption/desorption of ß-Ni(OH)2 through tailoring the 3d-orbital occupancy of Ni center by Co/Cu co-doping (denoted as Co-Cu-Ni(OH)2). Both experimental outcomes and density functional theory calculations validate that the co-doping of Co and Cu endows the Ni species in Co-Cu-Ni(OH)2 with appropriate proportion of the unoccupied 3d-orbital, leading to optimized adsorption/desorption strength of OH-. As anticipated, the Co-Cu-Ni(OH)2 electrode demonstrates superior performance, achieving an areal capacity of 0.83 mAh cm-2 and a gravimetric capacity of 164.3 mAh g-1 at ∼50 mA cm-2 (10 A g-1). Furthermore, it sustains an impressive capacity of 170.8 mAh g-1 (2.3 mAh cm-2) at a high mass loading of 13.5 mg cm-2, alongside a long-term cycling performance over 1000 cycles. The assembled Co-Cu-Ni(OH)2//Zn cell is able to provide a peak energy density of 0.98 mWh cm-2 and excellent durability. This work highlights the potential of an orbital engineering strategy in the development of next-generation high-capacity and durable energy storage materials.

Synergistic Release of Cd(II) and As(V) from Ternary Sorption Systems Containing Ferrihydrite Nanoparticles: The Role of Binary and Ternary Surface Complexes.

Cadmium (Cd) and arsenic (As) generally exhibit mutually beneficial co-sorption behavior on iron oxyhydroxides through multiple mechanisms, including surface precipitation, ternary surface complexes, and electrostatic interactions. However, the numerous factors that control the immobilization of Cd and As in turn complicated the processes and mechanisms involved in their co-desorption from iron minerals, which hindered the full understanding of their geochemical behaviors. Here, the simultaneous release of Cd(II) and As(V) from newly precipitated ferrihydrite nanoparticles by either Ca or P was investigated through kinetics and isothermal desorption experiments. We showed that the Cd(II) and As(V) present two-phase desorption processes (rapid desorption and slow desorption) in both binary (Fe-Cd or Fe-As alone) and ternary systems (Fe-Cd-As co-presence). Compared to their binary counterparts, Cd(II) and As(V) in the ternary systems are more prone to detachment from ferrihydrite. Further desorption of Cd(II) and As(V) at different co-presence scenarios (different initial concentrations) demonstrated mutual promotion behaviour towards their counterparts; the co-presence of Cd(II) facilitates the desorption of As(V), while the co-presence of As(V) also promotes the desorption of Cd(II). XPS and FTIR results demonstrated that either Ca or P showed minor effects on the binding environment of Cd and As. Further results from the in-situ ATR-FTIR experiment and second derivative peak fitting analysis indicate that the enhanced detachment of Cd(II) and As(V) from the ternary system may be due to the synergistic desorption of the ternary surface complexes and other surface complex species. Our results provide new insights into the prediction of the environmental behaviour of the coexistence of Cd(II) and As(V) in iron-rich geological settings. The potential environmental risks of iron-based remediation methods should be considered due to the enhanced bioavailability of Cd(II) and As(V) in co-presence circumstances.

Successful treatment of Staphylococcus argenteus sequence type 2198 uncomplicated bacteremia with a 2-week antibiotic course.

There is a paucity of data on the clinical course and treatment of Staphylococcus argenteus. Herein, we describe a successfully treated case of S. argenteus bacteremia. A 76-year-old man with lung adenocarcinoma developed bacteremia caused by penicillin-resistant, oxacillin-susceptible S. argenteus, which was identified through mass spectrometry and nuc gene sequencing. He was diagnosed with a peripheral line-associated bloodstream infection and successfully treated with a 2-week course of cefepime, followed by cefazolin, concurrent with intravenous catheter removal. The isolate was positive for blaZ and negative for mecA. It was assigned to sequence type 2198 using multilocus sequence typing. Formerly classified as Staphylococcus aureus clonal complex 75, S. argenteus became a distinct species in 2015. Its identification has increased owing to widespread mass spectrometer use. Most East and Southeast Asian S. argenteus isolates reported to date are methicillin-susceptible, consistent with the susceptibility pattern of the isolate in our study. Given the potential equivalence in virulence between S. argenteus and S. aureus, we recommend treating S. argenteus with the same rigor as S. aureus until further clinical data becomes available.

Investigation of interaction mechanism between polyvinyl chloride microplastics and phthalate acid esters using APGC-MS/MS.

Phthalate acid esters (PAEs) are a kind of typical endocrine disruptors chemicals (EDCs). PAEs can be enriched, migrated and released into organisms through microplastics (MPs), causing high toxicological risks. This study presented an atmospheric pressure gas chromatography-tandem mass spectrometry (APGC-MS/MS) method for 10 PAEs trace analysis. Based on this method, the interaction mechanism between polyvinyl chloride microplastics (PVC MPs) and PAEs was explored. The established APGC-MS/MS method achieved 10 PAEs analysis in 14 min with the satisfied detection limit as low as 0.0025 µg/L and excellent linearity (R2 = 0.99868-0.99996). The interaction mechanism investigation showed that PVC MPs had high adsorption and desorption capacities for PAEs. The adsorption mechanism involves adsorption distribution, surface adsorption, hydrophobic interaction and intermolecular van der Waals force. Temperature, diffusion channels, pore filling, hydrophobicity and solubilization may be potential desorption mechanisms. Moreover, the intestinal environment of warm-blood organisms has the highest bioavailability of PAEs. Overall, this APGC-MS/MS method of PAEs had the virtue of simplicity, efficiency, reliability and sensitivity, and could serve as a potential tool for risk analysis of MPs and PAEs exposure.

In-situ assembly of polyoxometalate-based metal-organic framework for high-efficiency recovery of uranium.

Extracting uranium from water is crucial for environmental protection and the sustainable nuclear power industry. However, high-efficiency extraction and mild desorption condition still poses significant challenges. Herein, a polyoxometalate-based metal-organic framework (POMOF) for high-performance uranium extraction is prepared by in situ confined encapsulating H3[PW12O40] (PW12) into MIL-101(Cr). The highly dispersed PW12 enables adsorption sites to be sufficiently exposed, supports the pore structure of MIL-101(Cr), while being protected by spatial confinement. Furthermore, its abundant oxygen groups form high-affinity coordination with uranium and provide the pH-dependent conformation switch to achieve selective adsorption and instantaneous structural transformation. The assembly of structure and function makes POMOF exhibit substantial synergistic stability and adsorption capacity. Consequently, the constructed MIL-101(Cr)@PW12 exhibits excellent uranium adsorption ability of 461.88 mg/g, as well as superior selectivity towards a wide variety of metal ions. Remarkably, instantaneous desorption can be achieved in 2 s under mild desorption conditions of 0.005 mol/L HCl, and the adsorption capacity remained at 94.30 % after 8 adsorption cycles. POMOF demonstrates the vast potential for uranium capture from water and offers new insight into designing structure and functional synergistic materials for the selective adsorption and instantaneous desorption of uranium.

Aligning Post-Column ESI-MS, MALDI-MS, and Coagulation Bioassay Data of Naja spp., Ophiophagus hannah, and Pseudonaja textillis Venoms Chromatographically to Assess MALDI-MS and ESI-MS Complementarity with Correlation of Bioactive Toxins to Mass Spectrometric Data.

Snakebite is a serious health issue in tropical and subtropical areas of the world and results in various pathologies, such as hemotoxicity, neurotoxicity, and local swelling, blistering, and tissue necrosis around the bite site. These pathologies may ultimately lead to permanent morbidity and may even be fatal. Understanding the chemical and biological properties of individual snake venom toxins is of great importance when developing a newer generation of safer and more effective snakebite treatments. Two main approaches to ionizing toxins prior to mass spectrometry (MS) analysis are electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI). In the present study, we investigated the use of both ESI-MS and MALDI-MS as complementary techniques for toxin characterization in venom research. We applied nanofractionation analytics to separate crude elapid venoms using reversed-phase liquid chromatography (RPLC) and high-resolution fractionation of the eluting toxins into 384-well plates, followed by online LC-ESI-MS measurements. To acquire clear comparisons between the two ionization approaches, offline MALDI-MS measurements were performed on the nanofractionated toxins. For comparison to the LC-ESI-MS data, we created so-called MALDI-MS chromatograms of each toxin. We also applied plasma coagulation assaying on 384-well plates with nanofractionated toxins to demonstrate parallel biochemical profiling within the workflow. The plotting of post-column acquired MALDI-MS data as so-called plotted MALDI-MS chromatograms to directly align the MALDI-MS data with ESI-MS extracted ion chromatograms allows the efficient correlation of intact mass toxin results from the two MS-based soft ionization approaches with coagulation bioassay chromatograms. This facilitates the efficient correlation of chromatographic bioassay peaks with the MS data. The correlated toxin masses from ESI-MS and/or MALDI-MS were all around 6-8 or 13-14 kDa, with one mass around 20 kDa. Between 24 and 67% of the toxins were observed with good intensity from both ionization methods, depending on the venom analyzed. All Naja venoms analyzed presented anticoagulation activity, whereas pro-coagulation was only observed for the Pseudonaja textillis venom. The data of MALDI-MS can provide complementary identification and characterization power for toxin research on elapid venoms next to ESI-MS.

Quantitive variation of male and female-specific compounds in 99 drosophilid flies.

Variation in sex pheromones is regarded as one of the causes of reproductive isolation and speciation. We recently identified 51 male- and female-specific compounds - many of which function as sex pheromones - in 99 drosophilid species [1]. Here, we report that despite many of these compounds being shared between species, their quantities differ significantly. For example, although 34 drosophilid species share the male-specific compound cis-vaccenyl acetate (cVA), which plays a critical role in regulating various social and sexual behaviors, the amount of cVA can differ by up to 600-fold between different species. Additionally, we found 7-tricosene, the cuticular hydrocarbon pheromone, present in 35 Drosophila species. Our findings indicate that 7-tricosene is equally present in both sexes of 14 species, more abundant in males of 14 species, and more abundant in females of 7 species. We provide raw data on the concentration of potential pheromone components in the 99 drosophilids, which can provide important insights for further research on the behavior and evolution of these species. Quantitative variations highlight species-specific patterns, suggesting an additional mechanism for reproductive isolation built on specific combinations of compounds at set concentrations.

Exploring the sorption/desorption of nitenpyram in loess soils: implications for neonicotinoid fate and ecological risk assessment.

Neonicotinoids are widely used insecticides that accumulate in various environmental matrixes and potentially harm non-target organisms. However, the mechanism of sorption/desorption of neonicotinoids in different loess soils remains poorly understood. Therefore, this study investigated the sorption/desorption of nitenpyram (NIT), a commonly used neonicotinoid, in three different types of loess soils and examined factors influencing the adsorption process using batch experiments. The findings revealed that NIT reached adsorption equilibrium in 4 h in all three loess soil samples. The R2 value (> 0.898) obtained from fitting the sorption/desorption kinetics indicated a good match with the pseudo-second-order model, suggesting the involvement of multiple mechanisms, including chemisorption. The linear and Freundlich models also adequately described the sorption of NIT in loess soils. Additionally, a clear hysteresis phenomenon was observed. The adsorption capacity of NIT is significantly related to the adsorption temperature, solution pH and ionic strength. Upon increasing the initial concentration, the equilibrium adsorption capacity of NIT for gray-cinnamon soil, sierozem, and cultivated loessial soil increased from 3.56, 2.51, and 2.64 mg/kg to 8.49, 3.92, and 5.22 mg/kg, respectively. FTIR spectral analysis revealed that the adsorption of NIT in loess soil was primarily governed by mixed mechanism. This study elucidates the behavior and fate of NIT in soil-water systems in the Northwest, while also establishing a foundation for assessing its ecological risks. The findings have significant practical implications for the future development of environmental management and pollution control strategies.

Iota-carrageenan as a regenerating system for Eu3+ recovery: adsorption/desorption cycles.

Renewable and biodegradable polysaccharides attract attention as environmentally friendly adsorbents for the removal of heavy metals from wastewater. One such group, is carrageenan, of which were recently successfully employed to adsorb representative lanthanide and actinide ions. Herein, iota-carrageenan-based hydrogels were used to adsorb europium ions (Eu3+) from water solutions, followed by desorption of the ions from the hydrogel beads and recycling of the beads three times. It was found that sorption yields from a 500 mg/L Eu3+ ion solution with beads that were prepared with 1 or 2 wt/v% aqueous solution of iota-carrageenan with CaCl2 (0.5 M) reached maximum sorption yield of 50% and 65%, correspondingly, after 1 h. In addition, the sorption kinetics followed the pseudo second-order model controlled by chemisorption. Desorption yields in the first cycle using NaNO3 (1 M) with both preparations were 57% and 74%, respectively. The sorption yields increased during the second and third cycles and were efficient in the overall pH range. Cryo-SEM, SEM, SEM-EDS and TGA analyses verified the adsorption and desorption of Eu3+ ions to and from the iota beads and that the Ca2+ ions that initially crosslinked the hydrogel were replaced during the cycles by Eu3+ or Na+ ions. In addition, the beads were stable and easily reusable for several sorption/desorption cycles. Furthermore, after sorption, the beads were characterised by a porous structure, such that beads prepared with a 2 wt/v% aqueous solution of iota-carrageenan yielded a more porous, ordered structure, and after desorption, the bead textures became even more porous.

Enhanced and robust nitrogen removal using an integrated zeolite and partial denitrification anammox process.

Anammox has received increased attention due to its enhanced and cost-efficient approach to nitrogen removal. However, its practical application is complicated by strict influent NO2--N to NH4+-N ratio demands and an 11% nitrate production from the anammox process. This study was the first known research to propose and verify a system of zeolite integrated with partial denitrification and anammox (Z-PDA) in an up-flow anaerobic sludge bed (UASB) reactor. The enhanced and robust nitrogen removal resulted in an ultra-high nitrogen removal efficiency (NRE, 93.0 ± 2.0%). Zeolite adsorption and biological desorption of ammonium contributed to robust nitrogen removal with fluctuating influent NO2--N to NH4+-N ratios. Applying 16S rRNA gene sequencing found that Candidatus Brocadia and Thauera were the key bacteria responsible for anammox and partial denitrification (PD), respectively. Zeolite also acted as a biological carrier. This significantly enriched anammox bacteria with a higher relative abundance of Candidatus Brocadia, reaching 49.2%. Metagenomic analysis demonstrated that the multiple functional genes related to nitrogen removal (nrfA/H, narG/H/I) and the metabolic pathways (Biosynthesis of cofactors, the Two-component system, the Biosynthesis of nucleotide sugars, and Purine metabolism) ensured the resilience of the Z-PDA system despite influent fluctuations. Overall, this study provided novel insights into the impacts of zeolite in the PDA system. It described the fundamental mechanism of zeolite based on adsorption and biological desorption, and demonstrated a meaningful application of the anammox process in sewage treatment.

Influence of cephalexin on cadmium adsorption onto microplastic particles in water: Human health risk evaluation.

This paper explores the impact of environmental factors on the adsorption of cadmium (Cd) and cephalexin (CEX) onto polyethylene (PE) microplastics. The study focused on Cd adsorption behavior on microplastics (MPs) of various sizes, revealing that particles sized 30-63 µm exhibited the highest adsorption capacity compared to other sizes. Cd sorption was significantly influenced by initial pH and salinity levels. Experimental data closely matched both the Langmuir (R2 > 0.91) and Freundlich (R2 > 0.92) isotherms. Cd adsorption onto PE particles was greater than CEX adsorption, with the maximum Cd uptake capacity measured at 1.8 mg/g. FTIR analysis indicated that Cd and CEX adsorption onto MPs was likely governed by physical interactions, as no new functional groups were detected post-uptake. The desorption rates of Cd and CEX from PE microplastics were evaluated in various liquids, including aqueous solution, tap water, seawater, and synthetic gastric juice. The health risks associated with Cd, in combination with MPs and CEX, for both children and adults were assessed in groundwater and aqueous solutions. This study offers scientific insights and guidelines for examining the environmental behavior, migration, and transformation of microplastics and their related ecological risks in scenarios of combined pollution.

Single-colony MALDI mass spectrometry imaging reveals spatial differences in metabolite abundance between natural and cultured Trichodesmium morphotypes.

Trichodesmium, a globally significant N2-fixing marine cyanobacterium, forms extensive surface blooms in nutrient-poor ocean regions. These blooms consist of a dynamic assemblage of Trichodesmium species that form distinct colony morphotypes and are inhabited by diverse microorganisms. Trichodesmium colony morphotypes vary in ecological niche, nutrient uptake, and organic molecule release, differentially impacting ocean carbon and nitrogen biogeochemical cycles. Here, we assessed the poorly studied spatial abundance of metabolites within and between three morphologically distinct Trichodesmium colonies collected from the Red Sea. We also compared these results with two morphotypes of the cultivable Trichodesmium strain IMS101. Using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) coupled with liquid extraction surface analysis (LESA) tandem mass spectrometry (MS2), we identified and localized a wide range of small metabolites associated with single-colony Trichodesmium morphotypes. Our untargeted MALDI-MSI approach revealed 80 unique features (metabolites) shared between Trichodesmium morphotypes. Discrimination analysis showed spatial variations in 57 shared metabolites, accounting for 62% of the observed variation between morphotypes. The greatest variations in metabolite abundance were observed between the cultured morphotypes compared to the natural colony morphotypes, suggesting substantial differences in metabolite production between the cultivable strain IMS101 and the naturally occurring colony morphotypes that the cultivable strain is meant to represent. This study highlights the variations in metabolite abundance between natural and cultured Trichodesmium morphotypes and provides valuable insights into metabolites common to morphologically distinct Trichodesmium colonies, offering a foundation for future targeted metabolomic investigations.IMPORTANCEThis work demonstrates that the application of spatial mass spectrometry imaging at single-colony resolution can successfully resolve metabolite differences between natural and cultured Trichodesmium morphotypes, shedding light on their distinct biochemical profiles. Understanding the morphological differences between Trichodesmium colonies is crucial because they impact nutrient uptake, organic molecule production, and carbon and nitrogen export, and subsequently influence ocean biogeochemical cycles. As such, our study serves as an important initial assessment of metabolite differences between distinct Trichodesmium colony types, identifying features that can serve as ideal candidates for future targeted metabolomic studies.

Generating pooled quality control samples of volatile organic compounds.

Untargeted analysis of volatile organic compounds (VOCs) from exhaled breath and culture headspace are influenced by several confounding factors not represented in reference standards. In this study, we propose a method of generating pooled quality control (QC) samples for untargeted VOC studies using a split-recollection workflow with thermal desorption tubes. Sample tubes were desorbed and split from each sample and recollected onto a single tube, generating a pooled QC sample. This QC sample was then repeatedly desorbed and recollected with a sequentially lower split ratio allowing injection of multiple QC samples. We found pooled QC samples to be representative of complex mixtures using principal component analysis and may be useful in future longitudinal, multi-centre, and validation studies to assess data quality and adjust for batch effects.

Adsorption-desorption mechanisms and migration behavior of fluchlordiniliprole in four different soils under varied conditions.

Utilizing infrared spectroscopy coupled with batch equilibrium methods, the adsorption and desorption characteristics of the novel Insecticide fluchlordiniliprole were assessed in four different soil types. It was found that fluchlordiniliprole's adsorption and desorption in these soils were consistent with the Freundlich isotherm, exhibiting adsorption capacities (KF-ads) ranging from 8.436 to 36.269. Temperature fluctuations, encompassing both high and low extremes, impaired the ability of soil to adsorb fluchlordiniliprole. In addition, adsorption dynamics were modulated by several other factors, including soil pH, ionic strength, amendments (e.g., biochar and humic substances), and the presence of various surfactants and microplastics. Although capable of leaching, fluchlordiniliprole exhibited weak mobility in most soils. Therefore, it appears that fluchlordiniliprole seems to pose a threat to surface soil and aquatic biota, but a minimal threat to groundwater. SYNOPSIS STATEMENT: This research examines the dynamics of fluchlordiniliprole in soil, an will aid in maintaining ecological safety and managing agricultural pesticides. The study's comprehensive analysis of adsorption, desorption, and soil migration patterns significantly contributes to our understanding of pesticide interactions with diverse soil types. The results of this study will enable the development of environmentally responsible agricultural practices.