Inferring the Molecular Basis for Dissolved Organic Matter Photochemical and Optical Properties.

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.

Role of Direct and Sensitized Photolysis in the Photomineralization of Dissolved Organic Matter and Model Chromophores to Carbon Dioxide.

This study addresses the fundamental processes that drive the photomineralization of dissolved organic matter (DOM) to carbon dioxide (CO2), deconvoluting the role of direct and sensitized photolysis. Here, a suite of DOM isolates and model compounds were exposed to simulated sunlight in the presence of various physical and chemical quenchers to assess the magnitude, rate, and extent of direct and sensitized photomineralization to CO2. Results suggest that CO2 formation occurs in a biphasic kinetic system, with fast production occurring within the first 3 h, followed by slower production thereafter. Notably, phenol model chromophores were the highest CO2 formers and, when conjugated with carboxylic functional groups, exhibited a high efficiency for CO2 formation relative to absorbed light. Simple polycarboxylated aromatic compounds included in this study were shown to be resistant to photomineralization. Quencher results suggest that direct photolysis and excited triplet state sensitization may be largely responsible for CO2 photoproduction in DOM, while singlet oxygen and hydroxyl radical sensitization may play a limited role. After 3 h of irradiation, the CO2 formation rate significantly decreased, and the role of sensitized reactions in CO2 formation increased. Together, the results from this study advance the understanding of the fundamental reactions driving DOM photomineralization to CO2, which is an important part of the global carbon cycle.

Decoupling Optical Response and Photochemical Formation of Singlet Oxygen in Size Isolated Fractions of Ozonated Dissolved Organic Matter.

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.

Computational Calculation of Dissolved Organic Matter Absorption Spectra.

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.

Photochemical Aging of Atmospheric Particulate Matter in the Aqueous Phase.

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.

Quenching of an Aniline Radical Cation by Dissolved Organic Matter and Phenols: A Laser Flash Photolysis Study.

Aromatic amines are relevant aquatic organic contaminants whose photochemical transformation is affected by dissolved organic matter (DOM). The goal of this study is to elucidate the underlying mechanism of the inhibitory effect of DOM on such reactions. The selected model aromatic amine, 4-(dimethylamino)benzonitrile (DMABN), was subjected to laser flash photolysis in the presence and absence of various model photosensitizers. The produced radical cation (DMABN•+) was observed to react with several phenols and different types of DOM on a time scale of ∼100 µs. The determined second-order rate constants for the quenching of DMABN•+ by phenols were in the range of (1.4-26) × 108 M-1 s-1 and increased with increasing electron donor character of the aromatic ring substituent. For DOM, quenching rate constants increased with the phenolic content of the DOM. These results indicate the reduction of DMABN•+ to re-form its parent compound as the basic reaction governing the inhibitory effect. In addition, the photosensitized oxidation of the sulfonamide antibiotic sulfadiazine (SDZ) was studied. The observed radical intermediate of SDZ was quenched by 4-methoxyphenol less effectively than DMABN•+, which was attributed to the lower reduction potential of the SDZ-derived radical compared to DMABN•+.

Laser flash photolysis study of the photoinduced oxidation of 4-(dimethylamino)benzonitrile (DMABN).

Aromatic amines are aquatic contaminants for which phototransformation in surface waters can be induced by excited triplet states of dissolved organic matter (3DOM*). The first reaction step is assumed to consist of a one-electron oxidation process of the amine to produce its radical cation. In this paper, we present laser flash photolysis investigations aimed at characterizing the photoinduced, aqueous phase one-electron oxidation of 4-(dimethylamino)benzonitrile (DMABN) as a representative of this contaminant class. The production of the radical cation of DMABN (DMABN˙+) after direct photoexcitation of DMABN at 266 nm was confirmed in accord with previous experimental results. Moreover, DMABN˙+ was shown to be produced from the reactions of several excited triplet photosensitizers (carbonyl compounds) with DMABN. Second-order rate constants for the quenching of the excited triplet states by DMABN were determined to fall in the range of 3 × 107-5 × 109 M-1 s-1, and their variation was interpreted in terms of electron transfer theory using a Rehm-Weller relationship. The decay kinetics of DMABN˙+ in the presence of oxygen was dominated by a second-order component attributed to its reaction with the superoxide radical anion (O2˙-). The first-order rate constant for the transformation of DMABN˙+ leading to photodegradation of DMABN was estimated not to exceed ≈5 × 103 s-1.

Effects of Ozone on the Photochemical and Photophysical Properties of Dissolved Organic Matter.

This study focused on the effects of ozonation on the photochemical and photophysical properties of dissolved organic matter (DOM). Upon ozonation, a decrease in DOM absorbance was observed in parallel with an increase in singlet oxygen (1O2) and fluorescence quantum yields (Φ1O2 and ΦF). The increase in Φ1O2 was attributed to the formation of quinone-like moieties during ozonation of the phenolic moieties of DOM, while the increase in ΦF can be explained by a significant decrease in the internal conversion rate of the first excited singlet state of the DOM (1DOM*). It is a consequence of an increase in the average energy of the first electronic transition (S1 → S0) that was assessed using the wavelength of maximum fluorescence emission (λF,max). Furthermore, ozonation did not affect the ratio of the apparent steady-state concentrations of excited triplet DOM (3DOM*) and 1O2, indicating that ozonation does not affect the efficiency of 1O2 production from 3DOM*. The consequences of these changes for the phototransformation rates of micropollutants in surface waters were examined using photochemical model calculations. The decrease in DOM absorbance caused by ozonation leads to an enhancement of direct photolysis rates due to the increased transparency of the water. Rates of indirect photooxidation induced by 1O2 and 3DOM* slightly decrease after ozonation.

Probing the Photosensitizing and Inhibitory Effects of Dissolved Organic Matter by Using N,N-dimethyl-4-cyanoaniline (DMABN).

Dissolved organic matter (DOM) can act as a photosensitizer and an inhibitor in the phototransformation of several nitrogen-containing organic contaminants in surface waters. The present study was performed to select a probe molecule that is suitable to measure these antagonistic properties of DOM. Out of nine studied nitrogen-containing aromatic compounds, 4-cyanoaniline, N,N-dimethyl-4-cyanoaniline (DMABN), sotalol (a ß-blocker) and sulfadiazine (a sulfonamide antibiotic) exhibited a marked photosensitized transformation that could be substantially inhibited by addition of phenol as a model antioxidant. The photosensitized transformation of DMABN, the selected probe compound, was characterized in detail under UV-A and visible irradiation (λ > 320 nm) to avoid direct phototransformation. Low reactivity of DMABN with singlet oxygen was found (second-order rate constant <2 × 107 M-1 s-1). Typically at least 85% of the reactivity of DMABN could be inhibited by DOM or the model antioxidant phenol. The photosensitized transformation of DMABN mainly proceeded (>72%) through demethylation yielding N-methyl-4-cyanoaniline and formaldehyde as primary products. In solutions of standard DOM extracts and their mixtures the phototransformation rate constant of DMABN was shown to vary nonlinearly with the DOM concentration. Model equations describing the dependence of such rate constants on DOM and model antioxidant concentrations were successfully used to fit experimental data.

The determination and prediction of the apparent reaction rates between excited triplet-state DOM and selected PPCPs.

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.

Assessing the source of the photochemical formation of hydroxylating species from dissolved organic matter using model sensitizers.

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.

Direct and indirect photodegradation of atrazine and S-metolachlor in agriculturally impacted surface water and associated C and N isotope fractionation.

Knowledge of direct and indirect photodegradation of pesticides and associated isotope fractionation can help to assess pesticide degradation in surface waters. Here, we investigated carbon (C) and nitrogen (N) isotope fractionation during direct and indirect photodegradation of the herbicides atrazine and S-metolachlor in synthetic agriculturally impacted surface waters containing nitrates (20 mg L-1) and dissolved organic matter (DOM, 5.4 mgC L-1). Atrazine and S-metolachlor were quickly photodegraded by both direct and indirect processes (half-lives <5 and <7 days, respectively). DOM slowed down photodegradation while nitrates increased degradation rates. The analysis of transformation products showed that oxidation mediated by hydroxyl radicals (HO˙) predominated during indirect photodegradation. UV light (254 nm) led to significant C and N isotope fractionation, yielding isotopic fractionation values εC = 2.7 ± 0.3 and 0.8 ± 0.1‰, and εN = 2.4 ± 0.3 and -2.6 ± 0.7‰ for atrazine and S-metolachlor, respectively. In contrast, photodegradation under simulated sunlight led to negligible C and slight N isotope fractionation, emphasizing the effect of the radiation wavelengths on the isotope fractionation induced by direct photodegradation. Altogether, these results highlight the importance of using simulated sunlight to obtain environmentally-relevant isotopic fractionation values and to distinguish photodegradation and other dissipation pathways in surface waters.