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1.
J AOAC Int ; 2024 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-38696770

RESUMO

BACKGROUND: Products containing humic acids (HA) and fulvic acids (FA) have significant commercial potential, however, unknown to the consumer, some products may be mislabeled or contain adulterants. The prevalence of mislabelling and adulterants is primarily found in FA products. Using UV-Vis spectroscopy to differentiate between real and fake FA products is practical and desirable. OBJECTIVE: The objective of this study was to expand the data set generated using a UV-VIS based method proposed by Mayhew et al., 2023. METHODS: In total, thirty (30) test samples were used to generate ninety test portions (3 replicates per test sample) for analysis using the UV-Vis methodology outlined in Mayhew et al., 2023, which in this study is referred to as the UVAC (UV absorbance confirmation) method. RESULTS: None of the thirteen FA test samples investigated were determined as humified using the UVAC method. The FA samples studied comprised of two IHSS standards, five commercial FA products (CFAP) and six full FA fractions (SFA), which were isolated from six known solid humic material sources (SHMS). There was a leonardite, a humalite, and four peat sources used as the SHMS. Analysis of the neutralized extract of the SHMS found only 3/6 SHMS were determined as humified. Six HA (SHA) test samples were also generated by isolating the HA from the SHMS and only 3/6 SHA were determined as humified. CONCLUSION: Given the high prevalence of false determinations more work is needed to improve the method so it can be used by industry or regulators. HIGHLIGHTS: The proposed method failed to determine IHSS FA standards as humified. Although the method is practical, it needs improvement and further study before it can be used for reliable differentiation of real from fake FA or HA.

2.
Environ Sci Technol ; 58(21): 9040-9050, 2024 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-38743693

RESUMO

Despite the widespread use of photochemical and optical properties to characterize dissolved organic matter (DOM), a significant gap persists in our understanding of the relationship among these properties. This study infers the molecular basis for the optical and photochemical properties of DOM using a comprehensive framework and known structural moieties within DOM. Utilizing Suwannee River Fulvic Acid (SRFA) as a model DOM, carboxylated aromatics, phenols, and quinones were identified as dominant contributors to the absorbance spectra, and phenols, quinones, aldehydes, and ketones were identified as major contributors to radiative energy pathways. It was estimated that chromophores constitute ∼63% w/w of dissolved organic carbon in SRFA and ∼47% w/w of overall SRFA. Notably, estimations indicate the pool of fluorescent compounds and photosensitizing compounds in SRFA are likely distinct from each other at wavelengths below 400 nm. This perspective offers a practical tool to aid in the identification of probable chemical groups when interpreting optical and photochemical data and challenges the current "black box" thinking. Instead, DOM photochemical and optical properties can be closely estimated by assuming the DOM is composed of a mixture of individual compounds.


Assuntos
Benzopiranos , Benzopiranos/química , Compostos Orgânicos/química , Rios/química
3.
Environ Sci Technol ; 58(6): 2798-2807, 2024 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-38294779

RESUMO

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.


Assuntos
Matéria Orgânica Dissolvida , Compostos Férricos , Espécies Reativas de Oxigênio , Superóxidos , Fotólise
8.
Sci Total Environ ; 881: 163117, 2023 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-37044337

RESUMO

To determine and predict the reaction rate between 3DOM* and PPCPs in various water bodies, this study defines a reaction rate coefficient ( [Formula: see text] ) to describe the reaction between 3DOM* and PPCPs. As the values also included the inhibition effect of DOM's antioxidant moieties, the calculation of [Formula: see text] is inconsistent with that of a bimolecular rate constant via the steady-state kinetic method. The [Formula: see text] values of 12 selected PPCPs were determined in two DOM solutions and ten DOM-containing water samples collected from typical surface water bodies in Beijing. The Pearson coefficients between nine predictors including the absorbance ratio (E2/E3), specific absorption coefficient at 254 nm (SUVA254), fluorescence index (FI), biological index (BIX), humification index (HIX), pH, total organic carbon (TOC), total fluorescence intensity (TFI) and TOC normalized TFI (TFI/TOC) and [Formula: see text] were examined. Correlation patterns for sulfonamides, ß-blockers and diclofenac supported the electron transfer pathway, and was distinctly different from those appeared for FQs where quenching effect played a main part. TFI and TFI/TOC were recognized as the most useful surrogates in empirically predicting [Formula: see text] . For PPCPs that went through the electron transfer pathway, [Formula: see text] could be well fit to the Rehm-Weller model assuming a proportional relationship between TFI and △Get. For FQs, [Formula: see text] was found to linearly correlated with TFI/TOC. The [Formula: see text] values determined in this study enrich the database of PPCPs photolysis parameters, and the correlation analysis provides reference for forecasting PPCPs fate in the aquatic environment.

9.
Environ Sci Technol ; 57(14): 5603-5610, 2023 04 11.
Artigo em Inglês | MEDLINE | ID: mdl-36977057

RESUMO

The complex effects of ozonation on the photophysical and size-based properties of dissolved organic matter (DOM) were investigated using two DOM isolates, Suwannee River Fulvic Acid (SRFA) and Pony Lake Fulvic Acid (PLFA). A size exclusion chromatography system paired with absorbance, fluorescence, and total organic carbon detection was used to determine the fluorescence quantum yield (Φf) as a function of the apparent molecular weight (AMW). Size-based fractions of each isolate were collected and irradiated to measure singlet oxygen (1O2) quantum yield (Φ1O2). Φf decreased with ozonation in low AMW fractions, while increasing in high AMW fractions. Φ1O2 increased with ozone dose in low AMW fractions from ∼2 to ∼7% and ∼3 to ∼11% for PLFA and SRFA, respectively, indicating that these are the most photoreactive fractions of DOM. Decreases in Φf and concomitant increases in Φ1O2 in low AMW fractions indicated that chemical transformations occurred, likely including the conversion of phenols to quinones, particularly in SRFA. Results further suggest that the photoactive and fluorescent fractions of DOM are likely independent pools of chromophores from different AMW fractions. In PLFA, a linear response in Φ1O2, specific UV absorbance at wavelength 254 nm (SUVA254), and Φf with ozonation indicated the equal distribution of ozone-reactive moieties.


Assuntos
Ozônio , Oxigênio Singlete , Oxigênio Singlete/química , Matéria Orgânica Dissolvida , Processos Fotoquímicos , Fenóis
12.
Environ Sci Technol ; 56(16): 11146-11161, 2022 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-35917372

RESUMO

Over the last 30 years, the optical property community has shifted from conducting dissolved organic matter (DOM) measurements on new complex mixtures in natural and engineered systems to furthering ecosystem understanding in the context of past, present, and future carbon (C) cycling regimes. However, the appropriate use of optical properties to understand DOM behavior in complex biogeochemical systems is of recent debate. This critical review provides an extensive survey of DOM optical property literature across atmospheric, marine, and terrestrial biospheres using a categorical approach that probes each biosphere and its subdivisions. Using this approach, a rubric of ecosystem variables, such as productive nature, C cycling rate, C inputs, and water quality, sets the foundation for interpreting commonly used optical property DOM metrics such as fluorescence index (FI), humification index (HIX), and specific ultraviolet absorbance at 254 nm (SUVA254). Case studies and a meta-analysis of each biosphere and subdivision found substantial overlap and characteristic distributions corresponding to ecosystem context for FI, HIX, and SUVA254, signifying chromophores and fluorophores from different ecosystems may be more similar than originally thought. This review challenges researchers to consider ecosystem connectivity when applying optical property results rather than making traditional "if this, then that" results-style conclusions.


Assuntos
Matéria Orgânica Dissolvida , Ecossistema , Carbono/análise , Compostos Orgânicos/análise , Espectrometria de Fluorescência/métodos , Qualidade da Água
13.
Environ Sci Technol ; 56(16): 11111-11131, 2022 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-35797184

RESUMO

Advanced oxidation processes (AOPs) can degrade a wide range of trace organic contaminants (TrOCs) to improve the quality of potable water or discharged wastewater effluents. Their effectiveness is impacted, however, by the dissolved organic matter (DOM) that is ubiquitous in all water sources. During the application of an AOP, DOM can scavenge radicals and/or block light penetration, therefore impacting their effectiveness toward contaminant transformation. The multiple ways in which different types or sources of DOM can impact oxidative water purification processes are critically reviewed. DOM can inhibit the degradation of TrOCs, but it can also enhance the formation and reactivity of useful radicals for contaminants elimination and alter the transformation pathways of contaminants. An in-depth analysis highlights the inhibitory effect of DOM on the degradation efficiency of TrOCs based on DOM's structure and optical properties and its reactivity toward oxidants as well as the synergistic contribution of DOM to the transformation of TrOCs from the analysis of DOM's redox properties and DOM's transient intermediates. AOPs can alter DOM structure properties as well as and influence types, mechanisms, and extent of oxidation byproducts formation. Research needs are proposed to advance practical understanding of how DOM can be exploited to improve oxidative water purification.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Matéria Orgânica Dissolvida , Oxirredução , Águas Residuárias/química , Poluentes Químicos da Água/química
14.
Environ Sci Process Impacts ; 24(8): 1110-1132, 2022 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-35789241

RESUMO

This review addresses the critical knowledge gap of techniques simulating combustion and heating characteristics present in natural wildfires and their use in assessing postfire impacts on water quality and quantity. Our assessment includes both laboratory and plot-scale techniques with burn and rainfall simulation components. Studies included focus on advancing understanding of changes in chemical and physical properties of soil, as well as subsequent runoff changes. Advantages of simulation experiments include: overcoming logistical challenges of collecting in situ wildfire data, reducing the high spatial variability observed in natural settings (i.e., the heterogeneity of burn intensity and the underlying vegetation and soil properties), and controlling the magnitude of key drivers of wildfire impacts. In sum, simulation experiments allow for more direct attribution of water quality and quantity responses to specific drivers than experiments conducted in situ. Drawbacks of simulation techniques include the limitation of observing only local-scale processes, the potential misrepresentation of natural settings (i.e., lack of spatial variability in vegetation, soil structure, burn intensity, etc.), uncertainty introduced through experimental error, and subsequent challenges in upscaling results to larger scales relevant for water management. This review focuses primarily on simulation techniques, with the goal of providing a foundation of knowledge for the design of future simulation experiments.


Assuntos
Incêndios Florestais , Solo , Qualidade da Água
16.
Environ Sci Technol ; 56(7): 4597-4609, 2022 04 05.
Artigo em Inglês | MEDLINE | ID: mdl-35262343

RESUMO

Wildfires in forested watersheds dramatically alter stored and labile soil organic matter (SOM) pools and the export of dissolved organic matter (DOM). Ecosystem recovery after wildfires depends on soil microbial communities and revegetation and therefore is limited by the availability of nutrients, such as nitrogen-containing and labile, water-soluble compounds. However, SOM byproducts produced at different wildfire intensities are poorly understood, leading to difficulties in assessing wildfire severity and predicting ecosystem recovery. In this work, water-extractable organic matter (WEOM) from laboratory microcosms of soil burned at discrete temperatures was characterized by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to study the impacts of fire temperature on SOM and DOM composition. The molecular composition derived from different burn temperatures indicated that nitrogen-containing byproducts were enriched with heating and composed of a wide range of aromatic features and oxidation states. Mass difference-based analysis also suggested that products formed during heating could be modeled using transformations along the Maillard reaction pathway. The enrichment of N-containing SOM and DOM at different soil burning intensities has important implications for ecosystem recovery and downstream water quality.


Assuntos
Microbiota , Incêndios Florestais , Reação de Maillard , Nitrogênio/análise , Solo/química
17.
Environ Sci Technol ; 56(1): 491-500, 2022 01 04.
Artigo em Inglês | MEDLINE | ID: mdl-34905334

RESUMO

The absorption spectrum of dissolved organic matter (DOM) is a topic of interest to environmental scientists and engineers as it can be used to assess both the concentration and physicochemical properties of DOM. In this study, the UV-vis spectra for DOM model compounds were calculated using time-dependent density functional theory. Summing these individual spectra, it was possible to re-create the observed exponential shape of the DOM absorption spectra. Additionally, by predicting the effects of sodium borohydride reduction on the model compounds and then calculating the UV-vis absorbance spectra of the reduced compounds, it was also possible to correctly predict the effects of borohydride reduction on DOM absorbance spectra with a relatively larger decrease in absorbance at longer wavelengths. The contribution of charge-transfer (CT) interactions to DOM absorption was also evaluated, and the calculations showed that intra-molecular CT interactions could take place, while inter-molecular CT interactions were proposed to be less likely to contribute.


Assuntos
Matéria Orgânica Dissolvida , Compostos Orgânicos , Compostos Orgânicos/química
18.
Environ Sci Process Impacts ; 24(1): 102-115, 2022 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-34908096

RESUMO

Dissolved organic matter (DOM) is ubiquitous in natural waters and can facilitate the chemical transformation of many contaminants through the photochemical production of reactive intermediates, such as singlet oxygen (1O2), excited triplet state DOM (3DOM*), and hydroxylating species (˙OH and other intermediates of similar reaction chemistry). The formation mechanism of most reactive intermediates is well understood, but this is not the case for the formation of hydroxylating species from DOM. To investigate this chemistry, DOM model sensitizers were irradiated with two different probe compounds (benzene and benzoic acid) at two irradiation wavelengths (254 and 320 nm). The ability of DOM model sensitizers to hydroxylate these arene probes was assessed by measuring rates of formation of the hydroxylated probe compounds (phenol and salicylic acid). Multiple classes of model sensitizers were tested, including quinones, hydroxybenzoic acids, aromatic ketones, and other triplet forming species. Of these classes of model sensitizers, only quinones and hydroxybenzoic acids had a hydroxylating capacity. Methanol quenching experiments were used to assess the reactivity of hydroxylating species. These results have several implications for the systems tested. First, they suggest that the hydroxylating intermediate produced from hydroxybenzoic acid photolysis may not be hydroxyl radical, but a different hydroxylating species. Also, these data prompted investigation of whether quinone photoproducts have a hydroxylating capacity. These results confirm that hydroxybenzoic acids and quinones are important to the photochemical production of hydroxylating species from DOM, but the mechanism by which this occurs for these classes of sensitizers is still elusive.


Assuntos
Compostos Orgânicos , Poluentes Químicos da Água , Matéria Orgânica Dissolvida , Radical Hidroxila , Processos Fotoquímicos , Fotólise
19.
Environ Sci Technol ; 55(19): 13152-13163, 2021 10 05.
Artigo em Inglês | MEDLINE | ID: mdl-34529399

RESUMO

This study focused on the photoaging of atmospheric particulate matter smaller than 2.5 µm (PM2.5) in the aqueous phase. PM2.5 was collected during a winter, a spring, and a summer campaign in urban and rural settings in Colorado and extracted into water. The aqueous extracts were photoirradiated using simulated sunlight, and the production rate (r•OH) and the effects of hydroxyl radicals (•OH) were measured as well as the optical properties as a function of the photoaging of the extracts. r•OH was seen to have a strong seasonality with low mean values for the winter and spring extracts (4.8 and 14 fM s-1 mgC-1 L, respectively) and a higher mean value for the summer extracts (65.4 fM s-1 mgC-1 L). For the winter extracts, •OH was seen to mostly originate from nitrate photolysis while for the summer extracts, a correlation was seen between r•OH and iron concentration. The extent of photobleaching of the extracts was correlated with r•OH, and the correlation also indicated that non-•OH processes took place. Using the •OH measurements and singlet oxygen (1O2) measurements, the half-life of a selection of compounds was modeled in the atmospheric aqueous phase to be between 1.9 and 434 h.


Assuntos
Óxidos de Nitrogênio , Material Particulado , Radical Hidroxila , Água
20.
Environ Sci Technol ; 55(16): 10928-10934, 2021 08 17.
Artigo em Inglês | MEDLINE | ID: mdl-34342987

RESUMO

Cyanobacteria populate most water environments, and their ability to effectively exploit light and nutrients provide them with a competitive advantage over other life forms. In particular conditions, cyanobacteria may experience considerable growth and give rise to the so-called harmful algal blooms (HABs). HABs are often characterized by the production of cyanotoxins, which cause adverse effects to both aquatic organisms and humans and even threaten drinking water supplies. The concentration of cyanotoxins in surface waters results from the budget between production by cyanobacteria and transformation, including photodegradation under sunlight exposure. Climate change will likely provide favorable conditions for HABs, which are expected to increase in frequency over both space and time. Moreover, climate change could modify the ability of some surface waters to induce phototransformation reactions. Photochemical modeling is here carried out for two cyanotoxins of known photoreaction kinetics (microcystin-LR and cylindrospermopsin), which follow different phototransformation pathways and for particular freshwater scenarios (summertime stratification in lakes, water browning, and evaporative water concentration). On this basis, it is possible to quantitatively predict that the expected changes in water-column conditions under a changing climate would enhance photodegradation of those cyanotoxins that are significantly transformed by reaction with the triplet states of chromophoric dissolved organic matter (3CDOM*). This is known to be the case for microcystin-LR, for which faster photodegradation in some environments would at least partially offset enhanced occurrence. Unfortunately, very few data are currently available for the role of 3CDOM* in the degradation of other cyanotoxins, which is a major knowledge gap in understanding the link between cyanotoxin photodegradation and changing climate.


Assuntos
Mudança Climática , Cianobactérias , Microcistinas , Proliferação Nociva de Algas , Lagos , Fotólise
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