Pahokee Peat Humic Acid Research Articles

Understanding the Interactions of Nanoparticles and Dissolved Organic Matter at the Molecular Level by 1H 2D Multi-Exponential Transverse Relaxation NMR Spectroscopy.

The interaction between humic acid (HA) and engineered nanoparticles (NPs) is critical in environmental sciences, especially for understanding the behavior of NPs in natural waters. This study employs 1H 2D Multi-Exponential Transverse Relaxation (METR) NMR spectroscopy to examine the molecular-level interactions between Pahokee Peat humic acid (HA) and carboxyl-functionalized iron oxide nanoparticles (NPCOs). First, 1H 2D METR NMR spectroscopy allowed not only the identification of HA in terms of its chemical composition but also the separation of molecules with the same chemical shift values but different rates of molecular tumbling. Then, using solutions with varying NPCO concentrations (0, 10, 40, and 100 μM), we observed significant changes in the T2 relaxation times of HA components, indicating interactions between HA and NPCO. Analysis showed the biggest effect on two chemical shift regions, corresponding to lipids and carbohydrates, revealing that smaller molecules within these regions exhibit the most significant changes in T2 values upon the addition of NPCO. This suggests that these molecules are the initial sites of interaction, with the entire HA system being affected at higher NPCO concentrations. These findings highlight the utility of METR NMR spectroscopy in studying complex environmental mixtures and provide insights into the behavior of HA and NPs, essential for understanding the fate of NPs in the environment.

Products from Photolysis Reactions of Tetracycline Mediated by Clay and Humic Substance Induce Contrasting Expressions of Target Resistance Genes.

Phototransformation is a key process affecting the fate of many antibiotics in the environment, but little is known about whether their photoproducts exert selective pressure on bacteria by inducing antibiotic resistance genes (ARGs). Here, we examined the expression of tetracycline resistance gene tet(M) of a fluorescent Escherichia coli whole-cell bioreporter influenced by the phototransformation of tetracycline. The presence of suspended smectite clay (montmorillonite or hectorite, 1.75 g/L) or dissolved humic substance (Pahokee Peat humic acid or Pahokee peat fulvic acid, 10 mg C/L) in aqueous solutions markedly facilitated the transformation of tetracycline (initially at 400 μg/L) with half-life shortened by 1.4-2.6 times. Despite the similar phototransformation ratios (80-90%) of the total loaded tetracycline after 60 min irradiation, the decreased ratios of cell fluorescence intensity (which was proportional to the expression amount of ARG tet(M)) were much higher with the two clays (94 and 93%) than with the two humic substances (44 and 69%) when compared to the respective dark controls. As illustrated by mass spectroscopic and chemical analyses, tetracycline was proposed to be mainly transformed to amide (ineffective in inducing ARGs) with the presence of clays by reaction with self-photosensitized singlet oxygen (1O2), while the humic substances might catalyze the production of another two demethylated and/or deaminated compounds (still effective in inducing ARGs) in addition to the amide compound via reaction with triplet excited state dissolved organic matter (3DOM*). As clay minerals and humic substances are important soil constituents and ubiquitously present in surface environments, the observed clay and humic-dependent photooxidation pathways of tetracycline and the differing selective pressures of the associated products highlight the need for monitoring the transformation compounds of antibiotics and provide critical insight into the development of antibiotic treatment protocols.

Dissolved organic matters-enhanced Pb releases from nano- or submicron Pb sulfides and oxides

Diverse lead (Pb) particles possess different ecological risks not only due to their own toxicity differences but also because of different abilities to release toxic dissolved Pb. Dissolved organic matter (DOM) was a key factor influencing dissolution processes of metal particles. However, impacts of DOM on dissolution of different Pb nano- or submicron particles were not known yet. Herein, impacts of DOM on dissolution kinetics of lead sulfide (PbS), lead sulfate (PbSO4), lead monoxide (PbO), lead tetroxide (Pb3O4) and lead dioxide (PbO2) nano- or submicron particles were firstly investigated taking Pahokee Peat humic acid (PPHA) as an example. Results indicated PPHA improved the suspending stability of Pb particles through electrostatic repulsion, and enhanced releases of dissolved Pb. Final concentration of dissolved Pb was raised by 1.22–8.82 times with PPHA. This was attributed to ligand exchange interactions between PPHA and Pb particles. Theoretical computations indicated that not only sorption or ligand exchange energy, but also numbers of ligands on the surface of particles were key factors governing impacts of PPHA on dissolved Pb. This study provided a new mechanism insight into dissolution behavior of various Pb particles and will be beneficial to their ecological risk assessment.

Effect of TOC Concentration of Humic Substances as an Electron Shuttle on Redox Functional Groups Stimulating Microbial Cr(VI) Reduction.

Humic substances as an electron shuttle play an essential role in the biogeochemistry processes. However, the influence of total organic carbon (TOC) concentrations of humic substances on microbial Cr(VI) reduction remains unclear. In this study, the rates and extents of Cr(VI) reduction by Shewanella oneidensis MR-1 in the presence of Leonardite humic acids (LHA) and Pahokee peat humic acids (PPHA) with different TOC concentrations were evaluated. We found that the enhanced reduction in Cr(VI) was associated with TOC concentrations of 2.5–50 mg C/L of HA samples. The result shows that HA as an electron shuttle impacted both rates and extents of microbial Cr (VI) reduction, which delivered differently in terms of low TOC concentration range of 2.5 to 15 mg C/L and high concentration range of 15–50 mg C/L. The rates of Cr(VI) reduction significantly enhanced in the low TOC concentration range of HA compared to a high concentration range. The highest acceleration rate of Cr(VI) reduction was achieved at 15 mg C/L of HA. The quinone-like fluorophore was responsible for the main redox-active functional groups of HA by the three-dimensional excitation-emission spectroscopy. The fluorescence intensity of quinone-like fluorophore of HA in the low TOC concentration range was positively correlated with its acceleration coefficient, corresponding to the highest microbial Cr(VI) reduction rate obtained in 15 mg C/L of HA. These findings highlighted the effect of the TOC concentration of HA on microbial Cr(VI) reduction processes. It emphasized that the low TOC concentration of HA contributed to the high rates of Cr(VI) reduction, which is critical for better understanding the fate of Cr(VI) and evaluating the effectiveness of Cr(VI) restoration strategies in the future.

Reduction of structural Fe(III) in nontronite by humic substances in the absence and presence of Shewanella putrefaciens and accompanying secondary mineralization

Abstract Studies have shown the electron shuttling role of humic substances (HS) in enhancing microbial reduction of solid-phase Fe(III), but it is unknown if native HS can reduce structural Fe(III) in clays and how their chemical properties affect this process and secondary mineralization. The objective of this study was to evaluate the role of natural HS, Leonardite humic acid (LHA), and Pahokee Peat humic acid (PPHA) in reducing structural Fe(III) in nontronite with or without Shewanella putrefaciens. The extent of Fe(III) reduction was determined with a wet chemical method. Electrochemical methods, spectroscopy, and mass spectrometry were used to determine the changes of HS electrochemical and molecular composition after bioreduction. X-ray diffraction and electron microscopy were used to observe mineralogical transformations. The results showed that natural HS not only served as an electron donor to abiotically reduce Fe(III) in nontronite but also served as an electron shuttle to enhance Fe(III) bioreduction by S. putrefaciens. In the presence of CN32 cells, both the rate and extent of Fe(III) reduction significantly increased. Between the two HS, PPHA was more effective. The final bioreduction extents were 12.2 and 17.8% with LHA and PPHA, respectively, in bicarbonate buffer. Interestingly, when CN32 cells were present, LHA and PPHA donated more electrons to NAu-2, suggesting that CN32 cells were able to make additional electrons of LHA and PPHA available to reduce structural Fe(III). Although LHA reduced less Fe(III), it induced more extensive mineral transformation. In contrast, PPHA reduced more Fe(III) but did not induce any mineralogical change. These contrasting behaviors between the two humic acids are ascribed to their differences in electron-donating capacity, reactive functional group distribution, and metal complexation capacity. A unique set of secondary minerals, including talc, illite, silica, albite, ilmenite, and ferrihydrite formed as a result of reduction. The results highlight the importance of coupled C and Fe biogeochemical transformations and have implications for nutrient cycling and contaminant migration in the environment.

Ligand Effects on Biotic and Abiotic Fe(II) Oxidation by the Microaerophile Sideroxydans lithotrophicus.

Organic ligands are widely distributed and can affect microbially driven Fe biogeochemical cycles, but effects on microbial iron oxidation have not been well quantified. Our work used a model microaerophilic Fe(II)-oxidizing bacterium Sideroxydans lithotrophicus ES-1 to quantify biotic Fe(II) oxidation rates in the presence of organic ligands at 0.02 atm O2 and pH 6.0. We used two common Fe chelators with different binding strengths: citrate (log KFe(II)-citrate = 3.20) and nitrilotriacetic acid (NTA) (log KFe(II)-NTA = 8.09) and two standard humic substances, Pahokee peat humic acid (PPHA) and Suwannee River fulvic acid (SRFA). Our results provide rate constants for biotic and abiotic Fe(II) oxidation over different ligand concentrations and furthermore demonstrate that various models and natural iron-binding ligands each have distinct effects on abiotic versus biotic Fe(II) oxidation rates. We show that NTA accelerates abiotic oxidation and citrate has negligible effects, making it a better laboratory chelator. The humic substances only affect biotic Fe(II) oxidation, via a combination of chelation and electron transfer. PPHA accelerates biotic Fe(II) oxidation, while SRFA decelerates or accelerates the rate depending on concentration. The specific nature of organic-Fe microbe interactions may play key roles in environmental Fe(II) oxidation, which have cascading influences on cycling of nutrients and contaminants that associate with Fe oxide minerals.

A significant correlation between kinetics of nitrobenzene reduction by sulfide and electron transfer capacity of mediating dissolved humic substances

Dissolved humic substances (DHS) are ubiquitous in surface and subsurface aquatic environments and greatly affect the redox transformation of organic contaminants as reactants and/or electron transfer mediators. However, little is known about the quantitative relationship between the mediation efficiency of DHS and the physicochemical properties of DHS. Using sulfide-induced nitrobenzene reduction as a model system, we measured the reduction rate of nitrobenzene in the presence of 12 different DHS (20 mgC·L−1), including 4 commercial humic substances (Suwannee River humic and fulvic acids and Pahokee Peat humic and fulvic acids) and 8 soil humic substances collected as leachates from a wide variety of soils. In addition to the UV–vis absorption and fluorescence spectra, the electron donating/accepting capacities (EDC/EAC) of the tested DHS were measured using an electrochemical approach. A significant linear correlation (r = 0.99, P < .0001) was observed between the observed pseudo-first-order rate constant (kobs) of nitrobenzene reduction and the sum of EDC and EAC which is defined as electron transfer capacity (ETC) of DHS. A relatively good positive correlation (r = 0.69, P < .2) was shown between the kobs and the specific UV-absorbance at 254 nm (SUVA254), whereas no good correlation was shown between the kobs and the fluorescence of the C1-C4 components identified by the excitation emission matrices and parallel factor (EEM-PARAFAC) analysis. This study provides a new framework for accurate prediction of the capability of DHS in mediating the redox transformation of organic contaminants. CapsuleA significant linear correlation exists between the kinetics of nitrobenzene reduction by sulfide and electron transfer capacity of mediating dissolved humic substances.

Differential absorbance study of interactions between europium, soil and aquatic NOM and model compounds

This study compared the binding of europium by soil and aquatic natural organic matter (NOM) exemplified by Pahokee Peat humic acid (PPHA) and Northern Reservoir NOM, respectively. NOM/Eu3+ interactions were measured based on the differential absorbance approach. The experimental results show that the binding of Eu3+ by humic acid isolated from agricultural soil results in several features of the differential spectra that are distinct from those observed for aquatic NOM. These features may be associated with the presence in soil NOM of functional groups similar to gallic acid. The binding of Eu3+ by NOM was modeled using a phenomenological approach that accounted for the involvement of dissimilar metal-binding functionalities. This study also introduced the concept of integrated differential absorbance; the use of that parameter allowed achieving a close fit between the experimental and model data. This study presents an alternative approach to ascertain mechanisms of, and differences in the interactions of europium with model compounds and natural organic matter with the provenance from soil and surface water.

Optical Properties of Humic Material Standards: Solution Phase and Aerosol Measurements

Aerosols generated from aqueous samples of readily obtainable humic material standards are often used as proxies for organic particulates found in the atmosphere in various investigations, such as consideration of radiative forcing effects. Here, we present results for the retrieved complex index of refraction, m = n + ik, at a wavelength of 403 nm for aerosols prepared from six humic material standards using a calibrated cavity ring-down spectrometer: a humic acid sodium salt, Pahokee peat humic and fulvic acids, Elliott soil humic and fulvic acids, and Suwannee river fulvic acid. In addition, we have conducted UV–vis spectrometric studies to measure the mass absorption coefficients, molar absorptivities, and absorption Angstrom exponents of bulk aqueous solutions of the humic materials. We find clear differences between the humic acid (HA) and fulvic acid (FA) samples with the HA having larger values for the imaginary part of the refractive index, k. The mean value for the HA samples is k = 0.170 while ...

Compound-specific short-chain carboxylic acids identified in a peat dissolved organic matter using high-resolution liquid chromatography–mass spectrometry

Dissolved natural organic matter (DNOM) is primarily composed of exuded or remnant biomolecules from plants and microorganisms. Labile amino acids and sugars have been well documented in the low molecular weight components of DNOM. However, little attention has been devoted to the isolation of labile short-chain carboxylic acids (SSCAs), which have demonstrated biogeochemical significance as sources of assimilable carbon, promoters of mineral dissolution, and ligands for metal complexation. Here we present an analytical method that identifies compound-specific SSCAs in a peat-derived DNOM isolate, Pahokee peat humic acid. Using high-resolution liquid chromatography (LC) coupled with high-accurate orbitrap mass spectrometry (MS), we targeted the identification of five SSCAs of different types: gluconate (a C6 monocarboxylic acid), citrate (a branched C6 tricarboxylic acid), 2-ketoglutarate (a C5 dicarboxylic acid), and malate and fumarate (C4 dicarboxylic acids). Following LC-separation and electrospray ionization, the compounds were annotated directly by orbitrap MS using their exact mass-over-charge (m/z) ions in the negative mode and their stoichiometric composition. Validated by LC–MS metabolite annotation in a bacterial matrix, we achieved identification of all five compounds in the peat DNOM isolate. Each targeted m/z channel also captured non-targeted compounds at different retention times, which represent isomers or different compounds. We found that the five targeted and the two non-targeted SSCAs identified collectively accounted for high parts-per-million to low parts-per-thousand of the total carbon, oxygen, or carboxyl content. Building on these findings, an important next step is to obtain a comprehensive profiling of SSCA structures in DNOM of different origins.

Electron transfer at microbe-humic substances interfaces: Electrochemical, microscopic and bacterial community characterizations

Soluble and colloidal humic substances (HSs) involved in microbial extracellular electron transfer (EET) have been extensively investigated. However, little is known regarding EET at HS adlayers that are bound or complexed to the surface of natural solids. Here, we investigated EET process on seven types of HS adlayers by forming electroactive biofilms (EABs) and monitoring the biocurrent generation. The HS immobilized surfaces were carried out by firstly modifying glassy carbon surfaces via electrochemical reduction of aryl diazonium salts to create amino-functionalized surfaces, and then various HSs were covalently bonded to these amino groups via linkage molecules. The results showed that the HS adlayers formed from Leonardite, Elliott Soil and Pahokee Peat humic acids (HAs) facilitated EET by forming more active EABs, whereas the Suwannee River and Aldrich HAs, Suwannee River and Pahokee Peat fulvic acids (FAs) hindered EET. The EET positively correlated with electron accepting capacity and wettability of the HSs, and negatively correlated with the polarity of the HSs, and only weakly correlated with electron donating capacity and zeta potential of the HSs. Microscopic images showed that the thickness and viability of the biofilms varied based on the HS properties. A microbial community structure analysis showed that all of the biofilms were dominated by Proteobacteria and selectively enriched in Firmicutes and Bacteroidetes. Our study indicated that the HS adlayers significantly affected microbial EET, and these results provide a more comprehensive understanding of the HSs involved biogeochemical and biotransformation processes.

Humic acid-enhanced illite and talc formation associated with microbial reduction of Fe(III) in nontronite

Humic substances are a chemically heterogeneous class of organic macromolecules ubiquitous in the environment and have been reported to function as an electron shuttle for microbial iron reduction. In most experimental research, synthetic quinone compounds (e.g., anthraquinone-2,6-disulfonate, AQDS) were used as the surrogate for humic substances. However, comparative studies of the differences between humic substances and AQDS in microbial reduction of iron-containing clay minerals and subsequent mineral transformations are rare. To achieve this goal, anaerobic batch experiments were performed in non-growth medium (bicarbonate buffered, pH=7.0), with lactate as the electron donor, iron-rich smectite (nontronite NAu-2) as the electron acceptor, and a typical dissimilatory iron reducing bacterium Shewanella oneidensis MR-1 as the reaction mediator in the absence or presence of electron shuttles (Pahokee peat humic acid and AQDS). Pahokee peat humic acid (PPHA) and AQDS were amended in the media to achieve similar electron-accepting capacity. Our results indicated that both PPHA and AQDS greatly enhanced the final extent of smectite reduction by S. oneidensis MR-1 but to a different extent. The reduction extent at the end of experiments was 27.5% with PPHA, lower than that with AQDS (34.1%). Combined mineralogical analyses showed the conversion of smectite to illite upon bioreduction of nontronite with PPHA or AQDS, but this reaction was facilitated to a higher degree by PPHA than by AQDS. Biogenic talc was also observed when NAu-2 was bio-reduced with PPHA.

Role of humic substances in the degradation pathways and residual antibacterial activity during the photodecomposition of the antibiotic ciprofloxacin in water

This study focuses on the photo-transformation, in presence of humic substances (HSs), of ciprofloxacin (CIP), a commonly-used fluoroquinolone antibiotic whose presence in aquatic ecosystems is a health hazard for humans and other living organisms. HSs from the International Humic Substances Society (Elliott humic acid and fulvic acid, Pahokee peat humic acid and Nordic lake) and a humic acid extracted from modified coal (HACM) were tested for their ability to photodegrade CIP. Based on kinetic and analytical studies, it was possible to establish an accelerating effect on the rate of CIP decomposition caused by the humic substances. This effect was associated with the photosensitized capacity of the HSs to facilitate energy transfer from an excited humic state to the ground state of ciprofloxacin. Except for Nordic lake, which experienced a lower positive effect, no significant differences in the CIP transformation were found among the different humic acids examined. The photochemistry of CIP can be modified by parameters such as pH, CIP or oxygen concentration. The irradiation of this antibiotic in the presence of HACM showed that antimicrobial activity was negligible after 14 h for E. coli and 24 h for S. aureus. In contrast, the antimicrobial activity was only slightly decreased after 24 h of irradiation by direct photolysis. Although mineralization of CIP irradiation in the presence of a HACM solution was not achieved, biodegradability was achieved after 12 h of irradiation, indicating that microorganisms within the environment can easily degrade CIP photochemical by-products.

Character of Humic Substances as a Predictor for Goethite Nanoparticle Reactivity and Aggregation.

Natural organic matter (NOM) is ubiquitous in surface water and groundwater and interacts strongly with mineral surfaces. The details of these interactions, as well as their impacts on mineral surface reactivity, are not well understood. In this work, both the reactivity and aggregation of goethite (α-FeOOH) nanoparticles were quantified in the presence of well-characterized humic substances. Results from monitoring the kinetics of reductive degradation of 4-chloronitrobenzene (4-ClNB) by Fe(II) adsorbed onto the goethite nanoparticles with and without added humic substances demonstrates that, in all cases, humic substances suppressed Fe(II)-goethite reactivity. The ranking of the standards from the least to most inhibitive was Pahokee Peat humic acid, Elliot Soil humic acid, Suwannee River humic acid, Suwannee River NOM, Suwannee River fulvic acid I, Suwannee River fulvic acid II, and Pahokee Peat fulvic acid. Correlations between eight characteristics (molecular weight, carboxyl concentration, and carbon, oxygen, nitrogen, aliphatic, heteroaliphatic, and aromatic content) and 4-ClNB degradation rate constants were observed. Faster kinetic rates of reductive degradation were observed with increased molecular weight and nitrogen, carbon, and aromatic content, and slower rates were observed with increased carboxyl concentration and oxygen, heteroaliphatic, and aliphatic content. With these correlations, improved predictions of the reactivity of Fe(II)-goethite with pollutants based on properties of the humic substances are possible.

Combination of a Copper-Ion Selective Electrode and Fluorometric Titration for the Determination of Copper(II) Ion Conditional Stability Constants of Humic Substances.

A fluorescence quenching model using copper(II) ion (Cu(2+)) ion selective electrode (Cu-ISE) is developed. It uses parallel factor analysis (PARAFAC) to model fluorescence excitation-emission matrices (EEMs) of humic acid (HA) samples titrated with Cu(2+) to resolve fluorescence response of fluorescent components to Cu(2+) titration. Meanwhile, Cu-ISE is employed to monitor free Cu(2+) concentration ([Cu]) at each titration step. The fluorescence response of each component is fit individually to a nonlinear function of [Cu] to find the Cu(2+) conditional stability constant for that component. This approach differs from other fluorescence quenching models, including the most up-to-date multi-response model that has a problematic assumption on Cu(2+) speciation, i.e., an assumption that total Cu(2+) present in samples is a sum of [Cu] and those bound by fluorescent components without taking into consideration the contribution of non-fluorescent organic ligands and inorganic ligands to speciation of Cu(2+). This paper employs the new approach to investigate Cu(2+) binding by Pahokee peat HA (PPHA) at pH values of 6.0, 7.0, and 8.0 buffered by phosphate or without buffer. Two fluorescent components (C1 and C2) were identified by PARAFAC. For the new quenching model, the conditional stability constants (logK1 and logK2) of the two components all increased with increasing pH. In buffered solutions, the new quenching model reported logK1 = 7.11, 7.89, 8.04 for C1 and logK2 = 7.04, 7.64, 8.11 for C2 at pH 6.0, 7.0, and 8.0, respectively, nearly two log units higher than the results of the multi-response model. Without buffer, logK1 and logK2 decreased but were still high (>7) at pH 8.0 (logK1 = 7.54, logK2 = 7.95), and all the values were at least 0.5 log unit higher than those (4.83 ~ 5.55) of the multi-response model. These observations indicate that the new quenching model is more intrinsically sensitive than the multi-response model in revealing strong fluorescent binding sites of PPHA in different experimental conditions. The new model was validated by testing it with a mixture of two fluorescing Cu(2+) chelating organic compounds, i.e., l-tryptophan and salicylic acid mixed with one non-fluorescent binding compound oxalic acid titrated with Cu(2+) at pH 5.0.

Dynamic silver speciation as studied with fluorous-phase ion-selective electrodes: Effect of natural organic matter on the toxicity and speciation of silver

The widespread application of silver in consumer products and the resulting contamination of natural environments with silver raise questions about the toxicity of Ag+ in the ecosystem. Natural organic matter, NOM, which is abundant in water supplies, soil, and sediments, can form stable complexes with Ag+, altering its bioavailability and toxicity. Herein, the extent and kinetics of Ag+ binding to NOM, matrix effects on Ag+ binding to NOM, and the effect of NOM on Ag+ toxicity to Shewanella oneidensis MR-1 (assessed by the BacLight viability assay) were quantitatively studied with fluorous-phase Ag+ ion-selective electrodes (ISEs). Our findings show fast kinetics of Ag+ and NOM binding, weak Ag+ binding for Suwannee River humic acid, fulvic acid, and aquatic NOM, and stronger Ag+ binding for Pony Lake fulvic acid and Pahokee Peat humic acid. We quantified the effects of matrix components and pH on Ag+ binding to NOM, showing that the extent of binding greatly depends on the environmental conditions. The effect of NOM on the toxicity of Ag+ does not correlate with the extent of Ag+ binding to NOM, and other forms of silver, such as Ag+ reduced by NOM, are critical for understanding the effect of NOM on Ag+ toxicity. This work also shows that fluorous-phase Ag+ ISEs are effective tools for studying Ag+ binding to NOM because they can be used in a time-resolved manner to monitor the activity of Ag+ in situ with high selectivity and without the need for extensive sample preparation.

A new insight into a problem of mediating effects of humic acids on binding and biological effects of organic pollutants in natural soil

A major focus of this manuscript is to investigate the molecular environment of soil where organic pollutants including an active functional group, such as amine, are bound to humic acids (HA). Close consideration has been taken to binding and biological effects of organic pollutants in natural soil mediated by HA in dependence on the amine base. The investigation is carried out using a method of spin labeling electron paramagnetic resonance (SL EPR). Spin labels (SL) 2,5,5-trimethyl-2-(3-aminophenyl)pyrrolidin-1-yloxy (Anilino-SL) and 4-Amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-Amino-TEMPO), as well as extracellular fungal laccase from Trametes versicolor, are applied to samples of chernozem, its HA and standard HA, such as Elliott Soil HA, Pahokee Peat HA, leonardite. It is shown that HA mediate the interaction of amines with soil through the partitioning of them among the different compartments of soil in dependence on the amine base. Both aliphatic and aromatic amines become immediately bound to soil organic matter but via different mechanisms. HA bind only the aromatic amines. Their binding sites are located in the hydrophobic and anaerobic compartments of soil. Moreover, spectroscopic analysis evidenced that a number of binding sites are limited, and aromatic amines attracted to hydrophobic compartments in the soil environment form here the ordered structure. Kinetic analysis of a temporal change in the concentration of bound and non-bound aromatic amines points at a pronounced diamagnetic effect of compartments where aromatic amines become bound. In contrast to amine with a weak base, the aliphatic amines are not influenced by HA and remain in an active soil part. Manuscript concludes that mediating effects of HA are first realized through their electrochemical property. They define and isolate pollutants with a definitive base that can be described using the Octanol-Water Partition Coefficient. This binding in turn defines a biological effect of organic pollutants including amine with a weak base via the oxygen factor that results in a decrease in the magnitude of aerobic soil biota and disbalance of the soil microorganism community.

Impact of Pahokee Peat humic acid and buffer identity on goethite aggregation and reactivity

High concentrations of Pahokee Peat humic acid block reactive sites resulting in well-dispersed and less reactive goethite nanoparticles.

Investigation of humic substance photosensitized reactions via carbon and hydrogen isotope fractionation.

Humic substances (HS) acting as photosensitizers can generate a variety of reactive species, such as OH radicals and excited triplet states ((3)HS*), promoting the degradation of organic compounds. Here, we apply compound-specific stable isotope analysis (CSIA) to characterize photosensitized mechanisms employing fuel oxygenates, such as methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE), as probes. In oxygenated aqueous media, Λ (Δδ(2)H/Δδ(13)C) values of 23 ± 3 and 21 ± 3 for ETBE obtained by photosensitization by Pahokee Peat Humic Acid (PPHA) and Suwannee River Fulvic Acid (SRFA), respectively, were in the range typical for H-abstraction by OH radicals generated by photolysis of H2O2 (Λ = 24 ± 2). However, (3)HS* may become a predominant reactive species upon the quenching of OH radicals (Λ = 14 ± 1), and this process can also play a key role in the degradation of ETBE by PPHA photosensitization in deoxygenated media (Λ = 11 ± 1). This is in agreement with a model photosensitization by rose bengal (RB(2-)) in deoxygenated aqueous solutions resulting in one-electron oxidation of ETBE (Λ = 14 ± 1). Our results demonstrate that the use of CSIA could open new avenues for the assessment of photosensitization pathways.

Humic Substances Enhance Chlorothalonil Phototransformation via Photoreduction and Energy Transfer

The photodegradation of chlorothalonil, a polychlorinated aromatic fungicide widely used in agriculture, was investigated under ultraviolet-visible irradiation in the presence and absence of different humic substances that significantly enhance the chlorothalonil phototransformation. On the basis of a kinetic model, an analytical study, the effect of scavengers, the chlorothalonil phosphorescence measurement, and varying irradiation conditions, it was possible to demonstrate that this accelerating effect is due to their capacity to reduce the chlorothalonil triplet state via H-donor reaction and to energy transfer from the triplet humic to ground state chlorothalonil. Energy transfer occurs at wavelengths below 450 nm and accounts for up to 30% of the reaction in deoxygenated medium upon irradiation with polychromatic light (300-450 nm). This process is more important with Elliott humic and fulvic acids and with humic acids extracted from natural carbonaceous material than with Nordic NOM and Pahokee peat humic acids. The obtained results are of high relevance to understanding the processes involved in chlorothalonil phototransformation and the photoreactivity of humic substances. Chlorothalonil is one of the rare molecules shown to react by energy transfer from excited humic substances.