RESUMEN
Molecular properties of soil humic acid (HA) can play an important role in the mechanisms regulating plant nutrient availability. This study explores how the structure of HA is altered by long-term treatment with different forms of swine manure and how these changes may influence nutrient availability. Liquid swine manure (LSM), solid swine manure (SSM), and swine manure compost (SMC) were applied to a calcareous soil over 17 years in a long-term soil fertility study. HA was extracted from site soil samples and analyzed using fluorescence spectroscopic techniques, including a Cu2+ quenching experiment, in order to assess differences in the structure and functionality of the soil organic matter (SOM) resulting from these different treatments. Emission spectra of the SSM-HA and SMC-HA are similar, while the LSM-HA is distinct. Procedures such as parallel factor analysis (PARAFAC) decomposition of emission-excitation matrices showed that structures in the SSM-HA and SMC-HA samples have lower complexity, whereas the structures of LSM-HA are of higher complexity. Interactions with Cu2+ at different pH levels indicate that the LSM-HA shows more dynamic conformational changes as well as stronger interactions and higher quenching efficiency compared to the other treatments. Conversely, SMC-HA demonstrates relatively stable binding constant (Ka) values across different pH levels. The binding constants and quenching efficiency of SSM-HA are significantly affected by changes in pH. This study shows distinct structural characteristics of HA formed under different manure management systems and provides valuable insights into how these variations may impact nutrient dynamics in soils.
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Perfluorinated alkyl substances (PFAS) are ubiquitous environmental contaminants that are widely used in consumer products and fire suppression foams. The presence of PFAS in ground and surface water can create a route for PFAS to enter the soil, exposing ecosystems (including agroecosystems), where they will move through the food web via biomagnification. The toxicity of PFAS to plants, particularly in agricultural ecosystems, is of emerging concern due to the application of biosolids that are often contaminated with PFAS. Nevertheless, due to the low concentrations of PFAS in most agricultural soils, the direct impact of PFAS on plant health is not well understood. We used 1 H-nuclear magnetic resonance (NMR) metabolomics to explore the effects of exposure of two key PFAS, perfluorooctanoic acid and perfluorooctanesulfonic acid, on Arabidopsis thaliana, a model organism. We found that Arabidopsis exhibited an accumulation of multiple metabolites, including soluble sugars (glucose and sucrose), multiple amino acids, and tri-carboxylic acid (TCA) cycle intermediates, suggesting that PFAS exposure impacts the metabolism of plants by causing an accumulation of stress-related amino acids and soluble sugars that drives increased activity of the TCA cycle. The present study shows that 1 H-NMR metabolomics is a viable tool for investigating changes in the metabolic profile of plants exposed to PFAS and can be used to illuminate the stress response of plants in a high-throughput, nonbiased manner. Environ Toxicol Chem 2023;42:663-672. © 2022 SETAC.
Asunto(s)
Ácidos Alcanesulfónicos , Arabidopsis , Fluorocarburos , Arabidopsis/metabolismo , Ecosistema , Ácidos Alcanesulfónicos/metabolismo , Fluorocarburos/metabolismo , Suelo , Plantas/metabolismo , Ácidos Carboxílicos , Aminoácidos , Espectroscopía de Resonancia MagnéticaRESUMEN
The development of effective remedial technologies for the destruction of environmental pollutants requires the ability to clearly monitor degradation processes. Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for understanding reaction progress; however, practical considerations often restrict the application of NMR spectroscopy as a tool to better understand the degradation of environmental pollutants. Chief among these restrictions is the limited access smaller environmental research labs and remediation companies have to suitable NMR facilities. Benchtop NMR spectroscopy is a low-cost and user-friendly approach to acquire much of the same information as conventional nuclear magnetic resonance (NMR) spectroscopy, albeit with reduced sensitivity and resolution. This paper explores the practical application of benchtop NMR spectroscopy to understand the degradation of perfluorooctanoic acid using sodium persulfate, a common reagent for the destruction of groundwater contaminants. It is found that Benchtop 19 F NMR spectroscopy is able to monitor the complete degradation of perfluorooctanoic acid into fluoride; however, the observation of intermediate degradation products formed, which can be observed using a conventional NMR spectrometer, cannot be readily distinguished from the parent compound when measurements are performed using the benchtop instrument. Under certain reaction conditions, the formation of fluorinated structures that are resistant to further degradation is readily observed. Overall, it is shown that benchtop 19 F NMR spectroscopy has potential as a quick and reliable tool to assist in the development of remedial technologies for the degradation of fluorinated contaminants.
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Non-aqueous-phase liquids (NAPLs), composed primarily of organic solvents and other immiscible liquids, can be found in the subsurface at many industrial sites. The chemical composition of NAPLs is often complex and, in many instances, difficult to fully characterize using conventional analytical techniques based on targeted compound analysis. Incomplete characterization of NAPLs leaves gaps in the understanding of the chemical profile at an impacted site. Previous work has shown that nuclear magnetic resonance (NMR) spectroscopy may be able to assist in the improved characterization of complex NAPL samples. In general, NMR spectroscopy provides an unbiased approach for the analysis of organic compounds because different classes of compounds are all treated and analyzed using the same methods. In addition, NMR spectroscopy provides unique structural information that can be used to elucidate unknowns. The present study describes the use of NMR spectroscopy as a nontargeted tool to characterize the composition of NAPLs collected from an impacted site. It is shown that NMR spectroscopy can be a complementary tool to be used in site assessments to help provide improved understanding of NAPL chemistry, leading to the development of improved conceptual site models and improved strategies for remedial and managerial activities at impacted sites. Environ Toxicol Chem 2019;00:1-9. © 2019 SETAC.
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Espectroscopía de Resonancia Magnética , Compuestos Orgánicos/química , Solventes/química , Espectroscopía de Resonancia Magnética con Carbono-13 , Cromatografía de Gases y Espectrometría de Masas , Espectroscopía de Protones por Resonancia MagnéticaRESUMEN
Nonaqueous phase liquids (NAPLs) located at the surface of the water table and/or below the water table are often a significant source for groundwater contamination near current or former commercial/industrial facilities. Due to the complex and long history of many industrial sites, these NAPLs often contain a complex mixture of contaminants and as such can be difficult to fully characterize using conventional analytical methods. Remediation and risk assessment activities at sites containing NAPLs may, subsequently, be hindered as the contamination profile may not be fully understood. This paper demonstrates the application of bench-scale 1 H nuclear magnetic resonance (NMR) spectroscopy as a practical tool to assist with the characterization of complex NAPLs. Here, a NAPL collected from a contaminated site situated near a former chemical manufacturing facility was analyzed using a combination of one-dimensional (1D) 1 H NMR spectroscopy and two-dimensional (2D) 1 H J-resolved spectroscopy (JRES). It is shown that 1D NMR experiments are useful in the rapid identification of the classes of compounds present, whereas 2D JRES NMR experiments are useful in identifying specific compounds. The use of benchtop NMR spectroscopy as a simple and cost effective tool to assist in the analysis of contaminated sites may help improve the practical characterization of many heavily contaminated sites and facilitate improved risk assessments and remedial strategies.
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A quantitative understanding of the dynamics of the interactions between organofluorine compounds and humic acids will contribute to an improved understanding of the role that Natural Organic Matter plays as a mediator in the fate, transport and distribution of these contaminants in the environment. Here, Nuclear Magnetic Resonance (NMR) spectroscopy-based diffusion measurements are used to estimate the association dynamics between dissolved humic acid and selected organofluorine compounds: pentafluoroaniline, pentafluorophenol, potassium perfluorooctane sulfonate, and perfluorooctanoic acid. Under the conditions used here, the strength of the association with humic acid increases linearly as temperature decreases for all compounds except for perfluorooctanoic acid, which exhibits divergent behavior with a non-linear decrease in the extent of interaction as temperature decreases. A general interaction mechanism controlled largely by desolvation effects is suggested for all compounds examined here except for perfluorooctanoic acid, which exhibits a specific mode of interaction consistent with a proteinaceous binding site. Reverse Heteronuclear Saturation Transfer Difference NMR is used to confirm the identity and nature of the humic acid binding sites.
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Sustancias Húmicas , Hidrocarburos Fluorados/química , Contaminantes Químicos del Agua/química , Espectroscopía de Resonancia Magnética , Temperatura , TermodinámicaRESUMEN
In this study we explore the relationship between solution pH and the distribution of the binding interactions at different domains of a dissolved humic acid (HA) for three xenobiotics: pentafluoroaniline (PFA), pentafluorophenol (PFP), and hexafluorobenzene (HFB). The components of HA where xenobiotic interactions occur are identified using the (1)H{(19)F} Reverse Heteronuclear Saturation Transfer Difference (RHSTD) Nuclear Magnetic Resonance (NMR) spectroscopy experiment. At low pH, PFA and PFP interact preferentially with aromatic components of HA. Increasing pH reduces this preference. Conversely, HFB interacts with all components of HA equally, across the entire pH range. The possible roles of both aromatic-specific interactions and conformational changes of HA behind these observations are explored. It is shown that T-oriented π-π interactions at π-electron accepting HA structures are slightly stronger for PFA and PFP than for HFB. Using DOSY NMR it is shown that the pH-dependence of the interactions is correlated with changes in the conformation of the carbohydrate components of HA rather than with the aromatic components. It is argued that the observed preference for aromatic HA is caused by restricted access to the non-aromatic components of HA at low pH. These HA components form tightly bound hydrophobic domains due to strong inter- and intra-molecular hydrogen bonds. At high pH, these structures open up, making them more available for interactions with polar compounds.
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Compuestos de Anilina/química , Fluorobencenos/química , Fluorocarburos/química , Sustancias Húmicas , Fenoles/química , Xenobióticos/química , Compuestos de Anilina/análisis , Fluorobencenos/análisis , Fluorocarburos/análisis , Concentración de Iones de Hidrógeno , Modelos Químicos , Fenoles/análisis , Xenobióticos/análisisRESUMEN
The chemical nature of xenobiotic binding sites in soils is of vital importance to environmental biogeochemistry. Interactions between xenobiotics and the naturally occurring organic constituents of soils are strongly correlated to environmental persistence, bioaccessibility, and ecotoxicity. Nevertheless, because of the complex structural and chemical heterogeneity of soils, studies of these interactions are most commonly performed indirectly, using correlative methods, fractionation, or chemical modification. Here we identify the organic components of an unmodified peat soil where some organofluorine xenobiotic compounds interact using direct molecular-level methods. Using (19)Fâ(1)H cross-polarization magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy, the (19)F nuclei of organofluorine compounds are used to induce observable transverse magnetization in the (1)H nuclei of organic components of the soil with which they interact after sorption. The observed (19)Fâ(1)H CP-MAS spectra and dynamics are compared to those produced using model soil organic compounds, lignin and albumin. It is found that lignin-like components can account for the interactions observed in this soil for heptafluoronaphthol (HFNap) while protein structures can account for the interactions observed for perfluorooctanoic acid (PFOA). This study employs novel comprehensive multi-phase (CMP) NMR technology that permits the application of solution-, gel-, and solid-state NMR experiments on intact soil samples in their swollen state.
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Compuestos de Flúor/química , Espectroscopía de Resonancia Magnética/métodos , Suelo/química , Albúminas/química , Albúminas/metabolismo , Sitios de Unión , Caprilatos/química , Caprilatos/metabolismo , Compuestos de Flúor/análisis , Compuestos de Flúor/metabolismo , Radioisótopos de Flúor , Fluorocarburos/química , Fluorocarburos/metabolismo , Sustancias Húmicas/análisis , Lignina/química , Lignina/metabolismoRESUMEN
Heterogeneous samples, such as soils, sediments, plants, tissues, foods and organisms, often contain liquid-, gel- and solid-like phases and it is the synergism between these phases that determine their environmental and biological properties. Studying each phase separately can perturb the sample, removing important structural information such as chemical interactions at the gel-solid interface, kinetics across boundaries and conformation in the natural state. In order to overcome these limitations a Comprehensive Multiphase-Nuclear Magnetic Resonance (CMP-NMR) probe has been developed, and is introduced here, that permits all bonds in all phases to be studied and differentiated in whole unaltered natural samples. The CMP-NMR probe is built with high power circuitry, Magic Angle Spinning (MAS), is fitted with a lock channel, pulse field gradients, and is fully susceptibility matched. Consequently, this novel NMR probe has to cover all HR-MAS aspects without compromising power handling to permit the full range of solution-, gel- and solid-state experiments available today. Using this technology, both structures and interactions can be studied independently in each phase as well as transfer/interactions between phases within a heterogeneous sample. This paper outlines some basic experimental approaches using a model heterogeneous multiphase sample containing liquid-, gel- and solid-like components in water, yielding separate (1)H and (13)C spectra for the different phases. In addition, (19)F performance is also addressed. To illustrate the capability of (19)F NMR soil samples, containing two different contaminants, are used, demonstrating a preliminary, but real-world application of this technology. This novel NMR approach possesses a great potential for the in situ study of natural samples in their native state.
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Mezclas Complejas/análisis , Mezclas Complejas/química , Espectroscopía de Resonancia Magnética/instrumentación , Espectroscopía de Resonancia Magnética/métodos , Transición de Fase , Manejo de Especímenes/instrumentación , Manejo de Especímenes/métodos , Diseño de Equipo , Análisis de Falla de EquipoRESUMEN
A combination of forward and reverse heteronuclear ((19)F/(1)H) saturation transfer difference (STD) nuclear magnetic resonance (NMR) spectroscopic techniques were applied to characterize the noncovalent interactions between perfluorinated aromatic xenobiotics and dissolved humic acid. These NMR techniques produce detailed molecular-level descriptions of weak noncovalent associations between components in complex environmental mixtures, allowing the mechanisms underlying these interactions to be explored; (19)F observed heteronuclear STD (H-STD) is used to describe the average molecular orientation of the xenobiotics during their interactions with humic acid, whereas (1)H observed reverse-heteronuclear STD (RH-STD) is used to both identify and quantify preferences exhibited by xenobiotics for interactions at different types of humic acid moieties. First, by using H-STD, it is shown that selected aromatic organofluorides orient with their nonfluorine functional groups (OH, NH(2), and COOH) directed away from humic acid during the interactions, suggesting that these functional groups are not specifically involved. Second, the RH-STD experiment is shown to be sensitive to subtle differences in preferred interaction sites in humic acid and is used here to demonstrate preferential interactions at aromatic humic acid sites for selected aromatic xenobiotics, C(10)F(7)OH, and C(6)F(4)X(2), (where X = F, OH, NH(2), NO(2), or COOH), that can be predicted from the electrostatic potential density maps of the xenobiotic.
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Sustancias Húmicas , Resonancia Magnética Nuclear Biomolecular/métodos , Contaminantes Químicos del Agua/química , Xenobióticos/química , Cinética , Soluciones/químicaRESUMEN
Interactions between dissolved peat humic acid and two structurally dissimilar organofluorine compounds, perfluoro-2-naphthol and perfluoro-octanoic acid, are probed using a novel (1)H{(19)F} Nuclear Magnetic Resonance (NMR) Spectroscopy technique based on the Saturation Transfer Difference (STD) experiment. This technique is used here to show selectively only those regions of the (1)H NMR spectrum of humic acid that arise from chemical constituents interacting with perfluorinated organic compounds. This approach provides a tool for high-resolution analysis of interactions between contaminants and soil organic matter (SOM) directly at the molecular level. Soil organic matter is a chemically heterogeneous mixture, and traditional techniques used to study sorption or binding phenomenon are unable to resolve multiple processes occurring simultaneously at distinct chemical moieties. Here, multiple interaction domains are identified based on known chemical constituents of humic acid, most notably from lignin- and protein-derived material. Specifically, perfluoro-2-naphthol is shown to interact with lignin, protein, and aliphatic material; however, preference is exhibited for lignin-derived domains, while perfluoro-octanoic acid exhibits near exclusive preference for the protein-derived domains of humic acid.