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1.
Environ Sci Technol ; 58(35): 15587-15597, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39163040

RESUMEN

The carbonyl functionality of natural organic matter (NOM) is poorly constrained. Here, we treated Suwannee River NOM (SRNOM) with ammonium acetate and sodium cyanoborohydride to convert ketone-containing compounds by reductive amination to their corresponding primary amines. The total dissolved nitrogen content increased by up to 275% after amination. Up to 30% of the molecular formulas of SRNOM contained isomers with ketone functionalities as detected by ultrahigh-resolution mass spectrometry. Most of these isomers contained one or two keto groups. At least 3.5% of the oxygen in SRNOM was bound in ketone moieties. The conversion of reacted compounds increased linearly with O/H values of molecular formulas and was predictable from the elemental composition. The mean conversion rate of reacted compounds nearly followed a log-normal distribution. This distribution and the predictability of the proportion of ketone-containing isomers solely based on the molecular formula indicated a stochastic distribution of ketones across SRNOM compounds. We obtained isotopically labeled amines by using 15N-labeled ammonium acetate, facilitating the identification of reaction products and enabling NMR spectroscopic analysis. 1H,15N HSQC NMR experiments of derivatized samples containing less than 20 µg of nitrogen confirmed the predominant formation of primary amines, as expected from the reaction pathway.


Asunto(s)
Cetonas , Cetonas/química , Compuestos Orgánicos/química
2.
J Am Soc Mass Spectrom ; 35(8): 1713-1725, 2024 Aug 07.
Artículo en Inglés | MEDLINE | ID: mdl-38950165

RESUMEN

Peatland fires emit organic carbon-rich particulate matter into the atmosphere. Boreal and Arctic peatlands are becoming more vulnerable to wildfires, resulting in a need for better understanding of the emissions of these special fires. Extractable, nonpolar, and low-polar organic aerosol species emitted from laboratory-based boreal and Arctic peat-burning experiments are analyzed by direct-infusion atmospheric pressure photoionization (APPI) ultrahigh-resolution mass spectrometry (UHRMS) and compared to time-resolved APPI UHRMS evolved gas analysis from the thermal analysis of peat under inert nitrogen (pyrolysis) and oxidative atmosphere. The chemical composition is characterized on a molecular level, revealing abundant aromatic compounds that partially contain oxygen, nitrogen, or sulfur and are formed at characteristic temperatures. Two main structural motifs are identified, single core and multicore, and their temperature-dependent formation is assigned to the thermal degradation of the lignocellulose building blocks and other parts of peat.

3.
Environ Sci Technol ; 58(31): 13772-13782, 2024 Aug 06.
Artículo en Inglés | MEDLINE | ID: mdl-39058895

RESUMEN

Dissolved organic matter (DOM), the most reactive fraction of forest soil organic matter, is increasingly impacted by wildfires worldwide. However, few studies have quantified the temporal changes in soil DOM quantity and quality after fire. Here, soil samples were collected after the Qipan Mountain Fire (3-36 months) from pairs of burned and unburned sites. DOM contents and characteristics were analyzed using carbon quantification and various spectroscopic and spectrometric techniques. Compared with the unburned sites, burned sites showed higher contents of bulk DOM and most DOM components 3 months after the fire but lower contents of them 6-36 months after the fire. During the sharp drop of DOM from 3 to 6 months after the fire, carboxyl-rich alicyclic molecule-like and highly unsaturated compounds had greater losses than condensed aromatics. Notably, the burned sites had consistently higher abundances of oxygen-poor dissolved black nitrogen and fluorescent DOM 3-36 months after the fire, particularly the abundance of pyrogenic C2 (excitation/emission maxima of <250/∼400 nm) that increased by 150% before gradually declining. This study advances the understanding of temporal variations in the effects of fire on different soil DOM components, which is crucial for future postfire environmental management.


Asunto(s)
Incendios , Suelo , Suelo/química , China , Incendios Forestales , Bosques
4.
J Hazard Mater ; 473: 134605, 2024 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-38768537

RESUMEN

Polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and heteroatom-containing analogues, constitute an important environmental contaminant class. For decades, limited numbers of priority PAHs have been routinely targeted in pollution investigations, however, there is growing awareness for the potential occurrence of thousands of PACs in the environment. In this study, untargeted Fourier transform ion cyclotron resonance mass spectrometry was used for the molecular characterisation of PACs in a sediment core from Chiswick Ait, in the River Thames, London, UK. Using complex mixture analysis approaches, including aromaticity index calculations, the number of molecular PAC components was determined for eight core depths, extending back to the 1930s. A maximum of 1676 molecular compositions representing PACs was detected at the depth corresponding to the 1950s, and a decline in PAC numbers was observed up the core. A case linking the PACs to London's coal consumption history is presented, alongside other possible sources, with some data features indicating pyrogenic origins. The overall core profile trend in PAC components, including compounds with oxygen, sulfur, nitrogen, and chlorine atoms, is shown to broadly correspond to the 16 priority PAH concentration profile trend previously determined for this core. These findings have implications for other industry-impacted environments.

5.
J Environ Sci (China) ; 144: 67-75, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-38802239

RESUMEN

Freeze-induced acceleration of I- oxidation and the consequent iodination of dissolved organic matter (DOM) contribute to the formation of organoiodine compounds (OICs) in cold regions. The formed OICs may be a potentially important source of risk and are very closely with the environment and human health. Herein, we investigated the acceleration effects of the freeze process on I- oxidation and the formation of OICs. In comparison to reactive iodine species (RIS) formed in aqueous solutions, I- oxidation and RIS formation were greatly enhanced in frozen solution and were affected by pH, and the content of I- and O2. Freeze-thaw process further promoted I- oxidation and the concentration of RIS reached 45.7 µmol/L after 6 freeze-thaw cycles. The consequent products of DOM iodination were greatly promoted in terms of both concentration and number. The total content of OICs ranged from 0.02 to 2.83 µmol/L under various conditions. About 183-1197 OICs were detected by Fourier transform ion cyclotron resonance mass spectrometry, and more than 96.2% contained one or two iodine atoms. Most OICs had aromatic structures and were formed via substitution and addition reactions. Our findings reveal an important formation pathway for OICs and shed light on the biogeochemical cycling of iodine in the natural aquatic environment.


Asunto(s)
Congelación , Yoduros , Oxidación-Reducción , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/análisis , Yoduros/química , Halogenación , Yodo/química
6.
Chemosphere ; 349: 141018, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38141671

RESUMEN

Oil sands process-affected water (OSPW) is a by-product of the extraction of bitumen, and volumes of OSPW have accumulated across the Alberta oil sands region due to the governments zero-discharge policy. Some dissolved organics in OSPW, including toxic naphthenic acids (NAs), can be biodegraded in oxic conditions, thereby reducing the toxicity of OSPW. While there has been much focus on degradation of NAs, the biodegradation of other dissolved organic chemicals by endogenous organisms remains understudied. Here, using the HPLC-ultrahigh resolution Orbitrap mass spectrometry, we examined the microbial biodegradation of dissolved organic acids in OSPW. Non-targeted analysis enabled the estimation of biodegradation rates for unique heteroatomic chemical classes detected in negative ion mode. The microcosm experiments were conducted with and without nutrient supplementation, and the changes in the microbial community over time were investigated. Without added nutrients, internal standard-adjusted intensities of all organics, including NAs, were largely unchanged. The addition of nutrients increased the biodegradation rate of O2- and SO2- chemical classes. While anoxic biodegradation can occur in tailings ponds and end pit lakes, microbial community analyses confirmed that the presence of oxygen stimulated biodegradation of the OSPW samples studied. We detected several aerobic hydrocarbon-degrading microbes (e.g., Pseudomonas and Brevundimonas), and microbes capable of degrading sulfur-containing hydrocarbons (e.g., Microbacterium). Microbial community diversity decreased over time with nutrient addition. Overall, the results from this study indicate that toxic dissolved organics beyond NAs can be biodegraded by endogenous organisms in OSPW, but reaffirms that biological treatment strategies require careful consideration of how nutrients and dissolved oxygen may impact efficacy.


Asunto(s)
Yacimiento de Petróleo y Gas , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/análisis , Compuestos Orgánicos , Ácidos Carboxílicos/química , Oxígeno/análisis
7.
Water Res ; 246: 120694, 2023 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-37832250

RESUMEN

Halogenated organic compounds (HOCs), widely present in various environments, are generally formed by natural processes (e.g., photochemical halogenation) and anthropogenic activities (e.g., water disinfection and anthropogenic discharge of HOCs), posing health and environmental risks. Therefore, in-depth knowledge of the molecular composition, transformation, and fate of HOCs is crucial to regulate and reduce their formation. Because of the extremely complex nature of HOCs and their precursors, the molecular composition of HOCs remains largely unknown. The Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the most powerful resolution and mass accuracy for the simultaneous molecular-level characterization of HOCs and their precursors. However, there is still a paucity of reviews regarding the comprehensive characterization of HOCs by FT-ICR MS. Based on the FT-ICR MS, the formation mechanism, sample pretreatment, and analysis methods were summarized for two typical HOCs classes, namely halogenated disinfection byproducts and per- and polyfluoroalkyl substances in this review. Moreover, we have highlighted data analysis methods and some typical applications of HOCs using FT-ICR MS and proposed suggestions for current issues. This review will deepen our understanding of the chemical characterization of HOCs and their formation mechanisms and transformation at the molecular level in aquatic systems, facilitating the application of the state-of-the-art FT-ICR MS in environmental and geochemical research.


Asunto(s)
Ciclotrones , Compuestos Orgánicos , Análisis de Fourier , Espectrometría de Masas , Compuestos Orgánicos/análisis , Agua
8.
Environ Sci Technol ; 57(37): 13948-13958, 2023 09 19.
Artículo en Inglés | MEDLINE | ID: mdl-37671477

RESUMEN

Humic-like substances (HULIS), known for their substantial impact on the atmosphere, are identified in marine diesel engine emissions obtained from five different fuels at two engine loads simulating real world scenarios as well as the application of wet sulfur scrubbers. The HULIS chemical composition is characterized by electrospray ionization (ESI) ultrahigh resolution mass spectrometry and shown to contain partially oxidized alkylated polycyclic aromatic compounds as well as partially oxidized aliphatic compounds, both including abundant nitrogen- and sulfur-containing species, and clearly different to HULIS emitted from biomass burning. Fuel properties such as sulfur content and aromaticity as well as the fuel combustion efficiency and engine mode are reflected in the observed HULIS composition. When the marine diesel engine is operated below the optimum engine settings, e.g., during maneuvering in harbors, HULIS-C emission factors are increased (262-893 mg kg-1), and a higher number of HULIS with a shift toward lower degree of oxidation and higher aromaticity is detected. Additionally, more aromatic and aliphatic CHOS compounds in HULIS were detected, especially for high-sulfur fuel combustion. The application of wet sulfur scrubbers decreased the HULIS-C emission factors by 4-49% but also led to the formation of new HULIS compounds. Overall, our results suggest the consideration of marine diesel engines as a relevant regional source of HULIS emissions.


Asunto(s)
Atmósfera , Navíos , Biomasa , Sustancias Húmicas , Azufre
9.
Water Res ; 243: 120392, 2023 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-37542781

RESUMEN

Detailed molecular composition of solid phase extracted dissolved organic matter (SPEDOM) collected from fractured-rock groundwater was compared to connected surface river water at two different watersheds in the unconfined chalk aquifer of Champagne in France using full scan ultrahigh resolution electrospray and photoionization Fourier transform ion cyclotron mass spectrometry (FT-ICR MS), Orbitrap tandem MS (MS/MS) and 1H magnetic resonance spectroscopy (NMR). 1H NMR spectroscopy indicated that groundwater SPEDOM carried a higher contribution of aliphatic compounds while surface river waters SPEDOM were enriched in carboxyl-rich alicyclic molecules (CRAM), acetate derivatives and oxygenated units. Furthermore, we show here that use of photoionization (APPI(+)) in aquifer studies is key, ionizing about eight times more compounds than ESI in surface river water samples, specifically targeting the dissolved organic nitrogen pool, accounting for more than 50% of the total molecular space, as well as a non-polar, more aromatic fraction; with little overlap with compounds detected by ESI(-) FT-ICR MS. On the other hand, groundwater SPEDOM samples did not show similar selectivity as less molecular diversity was observed in APPI compared to ESI. Mass-difference transformation networks (MDiNs) applied to ESI(-) and APPI(+) FT-ICR MS datasets provided an overview of the biogeochemical relationships within the aquifer, revealing chemical diversity and microbial/abiotic reactions. Finally, the combination of ESI(-) FT-ICR MS and detailed Orbitrap MS/MS analysis revealed a pool of polar, anthropogenic sulfur-containing surfactants in the groundwaters, likely originating from agricultural runoff. Overall, our study shows that in this aquifer, groundwater SPEDOM contains a significantly reduced pool of organic compounds compared to surface river waters, possibly related to a combination of lack of sunlight and adsorption of high O/C formulas to mineral surfaces.


Asunto(s)
Materia Orgánica Disuelta , Agua Subterránea , Espectrometría de Masas en Tándem , Oscuridad , Espectroscopía de Resonancia Magnética , Agua
10.
J Am Soc Mass Spectrom ; 34(8): 1813-1820, 2023 Aug 02.
Artículo en Inglés | MEDLINE | ID: mdl-37431968

RESUMEN

The interpretation of data and optimization spectral acquisition of dissolved organic matter (DOM) by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) have been challenging due to the varied instrument performances among laboratories and the complex chemical characteristics of DOM. However, a universal spectral optimization strategy for FT-ICR MS spectra is still unavailable. The results of this study showed that the number, intensity, and resolving power of all assigned peaks increased with the ion accumulation time (IAT) and DOM concentrations within a reasonable range. The space-charge effect induced by the excess ions in the ICR cell can deteriorate the data quality of the FT-ICR MS spectra, which could be inspected by examining the mass errors and intensity deviation of the monoisotopic and 13C-isotopic peaks based on the 13C-isotopic pattern. The maximum absolute mass error and 13C-isotopic pattern-based intensity deviation are two critical criteria for inspecting the space-charge effect, which was suggested to be 2.0 ppm and 20%, respectively. Therefore, a novel strategy based on the 13C-isotopic pattern has been proposed in this study to optimize the FT-ICR MS spectra of DOM based on their wide occurrence of monoisotopic and 13C-isotopic signals. This optimization strategy has laid the fundamentals for the method development of FT-ICR MS and could be extended to different FT-ICR MS instruments and various organic complex mixtures.

11.
Molecules ; 28(10)2023 May 19.
Artículo en Inglés | MEDLINE | ID: mdl-37241921

RESUMEN

Cottonseed is the second major product of cotton (Gossypium spp.) crops after fiber. Thus, the characterization and valorization of cottonseed are important parts of cotton utilization research. In this work, the nonpolar and polar fractions of glanded (Gd) cottonseed were sequentially extracted by 100% hexane and 80% ethanol aqueous solutions and subjected to 13C and 1H nuclear magnetic resonance (NMR) spectroscopy and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), respectively. The nonpolar (crude oil) extracts showed the characteristic NMR peak features of edible plant oils with the absence of ω-3 linolenic acid. Quantitative analysis revealed the percentage of polyunsaturated, monounsaturated, and saturated fatty acids as 48.7%, 16.9%, and 34.4%, respectively. Both general unsaturated fatty acid features and some specific olefinic compounds (e.g., oleic, linolenic, and gondonic acids) were found in the nonpolar fraction. In the polar extracts, FT-ICR MS detected 1673 formulas, with approximately 1/3 being potential phenolic compounds. Both the total and phenolic formulas fell mainly in the categories of lipid, peptide-like, carbohydrate, and lignin. A literature search and comparison further identifies some of these formulas as potential bioactive compounds. For example, one compound [2,5-dihydroxy-N'-(2,3,4-trihydroxybenzylidene) benzohydrazide] identified in the polar extracts is likely responsible for the anticancer function observed when used on human breast cancer cell lines. The chemical profile of the polar extracts provides a formulary for the exploration of bioactive component candidates derived from cottonseed for nutritive, health, and medical applications.


Asunto(s)
Aceite de Semillas de Algodón , Gossypium , Humanos , Aceite de Semillas de Algodón/química , Espectrometría de Masas , Ácidos Grasos , Extractos Vegetales
12.
Water Res ; 229: 119477, 2023 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-36528925

RESUMEN

Despite effluent organic matter (EfOM) being a major consumer of ozone during wastewater treatment, little is known about ozonation byproducts (OBPs) produced from EfOM. To unambiguously identify OBPs, heavy ozone was used to ozonate EfOM, resulting in 18O labeled and unlabeled OBPs. Labeled OBPs mostly represent a single 18O transfer and were classified as either direct or indirect OBPs based on the 18O/16O intensity ratios of the isotopologues. Of the 929 labeled OBPs, 84 were unequivocally classified as direct OBPs. The remainder suggest a major contribution by indirect, hydroxyl radical induced formation of OBPs in EfOM. Overall, labelled OBPs possess a low degree of unsaturation and contributed most to OBP peak intensity - marking them as potential end products. A few direct and indirect OBPs with high peak intensity containing 18O and heteroatoms (N, S) were fragmented with CID FT-ICR-MS/MS and screened for indicative neutral losses carrying heavy oxygen. The neutral loss screening was used to detect the 18O location on the OBP and indicate the original functional group in EfOM based on known reaction mechanisms. We identified sulfoxide and sulfonic acid functional groups in selected OBPs - implying the presence of reduced sulfur in EfOM molecules - while no evidence for nitrogen containing functional groups reacting with ozone was found.


Asunto(s)
Ozono , Contaminantes Químicos del Agua , Purificación del Agua , Marcaje Isotópico , Espectrometría de Masas en Tándem , Contaminantes Químicos del Agua/análisis , Oxígeno , Purificación del Agua/métodos
13.
Food Chem ; 403: 134404, 2023 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-36182850

RESUMEN

Roasting is a technological process in some food applications of agricultural products. To investigate the composition changes of the extractable functional/bioactive components of cottonseed, in this work, glandless cottonseed kernels were roasted at 110, 120, 140 and 150 °C for 15 min, respectively. The UV/vis data of the 80 % ethanol extracts found that roasting increased the level of phenolic compounds. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry of the extracts identified about 44 % to 55 % of total formulas as potential phenolic compounds. Roasting (up to 140 °C) mainly increased carbohydrate-, lignin-, and tannin-like compounds while lipid-like compounds decreased. The compositional changes at 150 °C were less than those at 140 °C, attributed to devolatilization at the higher temperature. The information of chemical profiling of cottonseed and the roasting impact would be greatly useful in enhanced utilization of cottonseed as nutrient and functional foods or food supplements.


Asunto(s)
Aceite de Semillas de Algodón , Ciclotrones , Aceite de Semillas de Algodón/química , Análisis de Fourier , Espectrometría de Masas/métodos , Lignina , Espectrometría de Masa por Ionización de Electrospray/métodos
14.
Molecules ; 27(22)2022 Nov 12.
Artículo en Inglés | MEDLINE | ID: mdl-36431897

RESUMEN

FT-ICR MS (Fourier-transform ion cyclotron resonance mass spectrometry) analysis has shown great potential to aid in the understanding of the extremely high molecular diversity of cloud water samples. The main goal of this work was to determine the differences in terms of formula assignment for analytical (i.e., measurement replicates) and experimental replicates of a given cloud water sample. The experimental replicates, obtained by solid phase extraction, were also compared to the results obtained for freeze-dried samples to evaluate whether the presence of salts interferes with the analysis. Two S/N ratios, generally adopted for atmospheric samples, were evaluated, and three different algorithms were used for assignment: DataAnalysis 5.3 (Bruker), Composer (Sierra Analytics), and MFAssignR (Chemical Advanced Resolution Methods Lab). In contrast to other works, we wanted to treat this comparison from the point of view of users, who usually must deal with a simple list of m/z ratios and intensity with limited access to the mass spectrum characteristics. The aim of this study was to establish a methodology for the treatment of atmospheric aqueous samples in light of the comparison of three different software programs, to enhance the possibility of data comparison within samples.


Asunto(s)
Extracción en Fase Sólida , Manejo de Especímenes , Espectrometría de Masas , Liofilización , Programas Informáticos
15.
Front Microbiol ; 13: 863686, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35694303

RESUMEN

Viruses are ubiquitously distributed in the marine environment, influencing microbial population dynamics and biogeochemical cycles on a large scale. Due to their small size, they fall into the oceanographic size-class definition of dissolved organic matter (DOM; <0.7 µm). The purpose of our study was to investigate if there is a detectable imprint of virus particles in natural DOM following standard sample preparation and molecular analysis routines using ultrahigh-resolution mass spectrometry (FT-ICR-MS). Therefore, we tested if a molecular signature deriving from virus particles can be detected in the DOM fingerprint of a bacterial culture upon prophage induction and of seawater containing the natural microbial community. Interestingly, the virus-mediated lysate of the infected bacterial culture differed from the cell material of a physically disrupted control culture in its molecular composition. Overall, a small subset of DOM compounds correlated significantly with virus abundances in the bacterial culture setup, accounting for <1% of the detected molecular formulae and <2% of the total signal intensity of the DOM dataset. These were phosphorus- and nitrogen-containing compounds and they were partially also detected in DOM samples from other studies that included high virus abundances. While some of these formulae matched with typical biomolecules that are constituents of viruses, others matched with bacterial cell wall components. Thus, the identified DOM molecular formulae were probably not solely derived from virus particles but were partially also derived from processes such as the virus-mediated bacterial cell lysis. Our results indicate that a virus-derived DOM signature is part of the natural DOM and barely detectable within the analytical window of ultrahigh-resolution mass spectrometry when a high natural background is present.

16.
Water Res ; 216: 118336, 2022 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-35378451

RESUMEN

The presence of dissolved organic nitrogen (DON) in biological nutrient removal (BNR) effluent has led to increased concern about its adverse effects on wastewater discharge and reuse applications. Previous studies have demonstrated efficient biological inorganic nitrogen removal in BNR under low dissolved oxygen (DO) conditions; however, information on DON is scarce. This study investigated low-DO effects on DON and N-nitrosodimethylamine (NDMA) precursor concentrations in BNR effluents. Identical BNR reactors consisting of an external real-time DO intelligent control system were operated at three different DO concentrations (0.3, 1.0, and 4.0 mgO2/L). Surprisingly, significantly higher values of effluent DON (p<0.05, t-test) and NDMA precursors (p<0.01, t-test) were observed at lower DO levels. Ultrahigh-resolution mass spectrometry analysis showed that molecules produced by microbes at low-DO levels exhibited high proteins/amino sugars-like and low normal oxidation state of carbon characteristics, which possibly acted critical roles in NDMA formation. Furthermore, path analysis by partial least-squares path modeling suggested that NDMA formation potential had strong associations with microbe-DON network stability of microbe-DON co-occurrence interactions (r=0.979, p<0.01). These results highlight the necessity of reconsidering the feasibility of BNR systems operating at low-DO concentrations considering the adverse effects of DON on wastewater discharge and reuse applications.


Asunto(s)
Dimetilnitrosamina , Aguas Residuales , Materia Orgánica Disuelta , Nitrógeno/análisis , Nutrientes/análisis , Oxígeno/análisis , Aguas Residuales/análisis
17.
Environ Sci Technol ; 56(3): 1894-1904, 2022 02 01.
Artículo en Inglés | MEDLINE | ID: mdl-35007417

RESUMEN

Effluent organic matter (EfOM), a major ozone consumer during wastewater ozonation, is a complex mixture of natural and anthropogenic organic molecules. Ozonation of EfOM adds to molecular complexity by introducing polar and potentially mobile ozonation byproducts (OBPs). Currently, nontargeted direct infusion (DI) ultrahigh resolution mass spectrometry (e.g. FT-ICR-MS) is used to study OBPs but requires sample extraction, limiting the accessible polarity range of OBPs. To better understand the impact of ozonation on EfOM and the formation of polar OBPs, nonextracted effluent was analyzed by direct injection onto a reversed-phase liquid chromatography system (RP-LC) online hyphenated with an FT-ICR-MS. Over four times more OBPs were detected in nonextracted EfOM compared to effluent extracted with solid phase extraction and measured with DI-FT-ICR-MS (13817 vs 3075). Over 1500 highly oxygenated OBPs were detected exclusively in early eluting fractions of nonextracted EfOM, indicating polar OBPs. Oxygenation of these newly discovered OBPs is higher than previously found, with an average molecular DBE-O value of -3.3 and O/C ratio of 0.84 in the earliest eluting OBP fractions. These polar OBPs are consistently lost during extraction but may play an important role in understanding the environmental impact of ozonated EfOM. Moreover, 316 molecular formulas classified as nonreactive to ozone in DI-FT-ICR-MS can be identified with LC-FT-ICR-MS as isomers with varying degrees of reactivity, providing for the first time experimental evidence of differential reactivity of complex organic matter isomers with ozone.


Asunto(s)
Ozono , Contaminantes Químicos del Agua , Purificación del Agua , Espectrometría de Masas , Ozono/química , Extracción en Fase Sólida , Aguas Residuales/química , Contaminantes Químicos del Agua/química , Purificación del Agua/métodos
18.
Anal Bioanal Chem ; 414(8): 2687-2698, 2022 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-35075513

RESUMEN

To enhance the characterization of wood extractives at molecular level, a detailed ultrahigh-resolution mass spectrometry (UHRMS)-based analytical methodology was developed in this work. The analytical strategies, including selection of compatible solvent for extraction, evaluation of ionization solvent for effective electrospray ionization, and multi-dimensional data analysis, were established to ensure a comprehensive characterization of complex compositions in wood extractives. Extraction capability of seven solvents with varied polarities was examined by a standard reference material of hardwood biomass and evaluated based on thousands of compounds which were much more than those discovered before. With a variety of data-processing approaches, including compound type distribution, double bond equivalent versus carbon number plot, and van Krevelen diagram, the chemodiversity of the extractives was fully explored from different perspectives. This work greatly expanded the compound library of wood extractives and could also provide guidance for the integrated composition analysis of other biomass materials.


Asunto(s)
Madera , Biomasa , Espectrometría de Masas , Solventes/química , Madera/química
19.
Sci Total Environ ; 805: 150058, 2022 Jan 20.
Artículo en Inglés | MEDLINE | ID: mdl-34537690

RESUMEN

The co-occurrence of cyanobacterial harmful algal blooms and contaminants is an increasing environmental concern in freshwater worldwide. Our field investigations coupled with laboratory incubations demonstrated that the microbial degradation potential of 17ß-estradiol (E2) with estrone as the intermediate was primarily driven by increased dissolved organic matter (DOM) in the water column of a cyanobacterial bloom. To explain the intrinsic contribution of cyanobacterial-derived DOM (C-DOM) to estrogen biodegradation, a combination of methods including bioassay, ultrahigh-resolution mass spectrometry, and microbial ecology were applied. The results showed that preferential assimilation of highly biodegradable structures, including protein-, carbohydrate-, and unsaturated hydrocarbon-like molecules sustained bacterial growth, selected for more diverse microbes, and resulted in greater estrogen biodegradation compared to less biodegradable molecules (lignin- and tannin-like molecules). The biodegradability of C-DOM decreased from 78% to 1%, whereas the E2 biodegradation rate decreased dramatically at first, then increased with the accumulation of recalcitrant, bio-produced lipid-like molecules in C-DOM. This change was linked to alternative substrate-induced selection of the bacterial community under highly refractory conditions, as suggested by the greater biomass-normalized E2 biodegradation rate after a 24-h lag phase. In addition to the increased frequency of potential degraders, such as Sphingobacterium, the network analysis revealed that C-DOM molecules distributed in high H/C (protein- and lipid-like molecules) were the main drivers structuring the bacterial community, inducing strong deterministic selection of the community assemblage and upregulating the metabolic capacity for contaminants. These findings provide strong evidence that estrogen biodegradation in eutrophic water may be facilitated by cyanobacterial blooms and provide a theoretical basis for ecological remediation of estrogen pollution.


Asunto(s)
Cianobacterias , Lagos , Estrógenos , Estrona , Agua
20.
Mar Drugs ; 21(1)2022 Dec 22.
Artículo en Inglés | MEDLINE | ID: mdl-36662178

RESUMEN

The biochemical composition, molecular diversity, and two different bioactivities of Asparagopsis armata and Rugulopteryx okamurae (two alien species with different invasive patterns in the southern Iberian Peninsula) were analyzed through spectrophotometric methods and Fourier transform ion cyclotron mass spectroscopy (FT-ICR-MS). A total of 3042 molecular formulas were identified from the different extracts. The dH2O extracts were the most molecularly different. A. armata presented the highest content of nitrogenous compounds (proteins, CHON) and sulphur content, whereas R. okamurae was rich in carbonated compounds (total carbon, lipids, CHO, and CHOP). Antioxidant capacity and phenolic content were higher in R. okamurae than in A. armata. Antimicrobial activity was detected from both species. A. armata showed capacity to inhibit human and fish pathogens (e.g., Staphylococcus aureus or Vibrio anguillarum), whereas R. okamurae only showed inhibition against human bacteria (Staphylococcus aureus and Cutibacterium acnes). In R. okamurae, molecules with a great number of pharmaceutical activities (e.g., anti-inflammatory or antitumoral), antibacterial, biomaterial, and other utilities were found. The main molecules of A. armata had also pharmaceutical applications (e.g., antimalarian, antithrombotic, anti-inflammatory, or antiarthritis). The valorization of these species can help to counteract the environmental effects of the bioinvasions.


Asunto(s)
Phaeophyceae , Rhodophyta , Animales , Humanos , Especies Introducidas , Antibacterianos/farmacología , Antioxidantes/farmacología , Preparaciones Farmacéuticas , Extractos Vegetales/farmacología , Extractos Vegetales/química
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