Dissolved Organic Matter Singlet Oxygen Quantum Yields: Evaluation Using Time-Resolved Singlet Oxygen Phosphorescence.

Singlet oxygen (1O2) generation quantum yields from chromophoric dissolved organic matter (CDOM) have been reported for many samples over the past 4 decades. Yet even for standardized isolates such as those from the International Humic Substance Society (IHSS), wide-ranging values exist in the literature. In this manuscript, time-resolved 1O2 phosphorescence was used to determine the 1O2 quantum yields (ΦΔ) of a variety of dissolved organic matter (DOM) isolates and natural waters. In general, the 1O2 quantum yield values in this study are in the middle, although below the median of the range of past reported values (e.g., for Suwannee River Natural Organic Matter IHSS isolate: 1.8% vs 0.23-2.89%). Notably, hydrophobic neutral fractions of DOM isolates were found to possess the highest 1O2 quantum yields, an interesting result given that these fractions are not retained in typical humic and fulvic acid isolation procedures that use XAD resins. The excitation wavelength dependence of 1O2 generation from CDOM was also examined, and an approximate linear decrease with longer excitation wavelength was observed. This work advances the understanding of CDOM photoprocesses, especially in relation to wavelength-dependent 1O2 production, which is valuable for assessing real-world environmental behavior.

Quantifying photo-production of triplet excited states and singlet oxygen from effluent organic matter.

The organic matter present in wastewater effluents (EfOM), is likely to have different properties than the organic matter present in the receiving water. The properties of EfOM will affect the fate of contaminants of emerging concern because EfOM is a source of photochemically produced reactive intermediates (PPRIs) capable of transforming contaminants. Effluent water samples were taken seasonally from sixteen wastewater treatment plants in Minnesota and two effluent dominated rivers in California and Arizona. Samples (n = 94) were tested for water chemistry, light absorption characteristics, and excited state triplet organic matter (3EfOM∗) and singlet oxygen (1O2) production. Based on analysis of spectral parameters, EfOM had higher molecular weight and lower aromatic content than organic matter present in stormwaters from Minnesota, which are representative of human-impacted natural organic matter (NOM) containing waters. The second order rate constant for the reaction of the 3EfOM∗ probe 2,4,6-trimethylephenol (kT,TMP) for the effluents was 7.79 (±3.03) × 108 M-1s-1, and this value was used to calculate apparent quantum yields for 3EfOM∗ production, which ranged from 0.006 to 0.114. The quantum yield for the production of singlet oxygen ranged from 0.007 to 0.064. Processes in the wastewater treatment train, season, and water chemistry parameters did not serve as predictors of 3EfOM∗ or 1O2 production. Among the parameters measured, Spearman rank correlations were strongest between quantum yields of 1O2 and 3EfOM∗ and E2/E3 (absorption at 250 nm/absorption at 365 nm). This relationship, however, is weaker than that previously observed for NOM. The efficiency of 1O2 production from 3EfOM∗ was 54%. Results indicate that 2,4,6-trimethylphenol samples nearly all of the triplets in EfOM that have sufficient energy to produce 1O2, which may not be the case for NOM.

Singlet Oxygen Phosphorescence as a Probe for Triplet-State Dissolved Organic Matter Reactivity.

Triplet-state chromophoric dissolved organic matter (3CDOM*) plays an important role in aquatic photochemistry, yet much remains unknown about the reactivity of these intermediates. To better understand the kinetic behavior and reactivity of 3CDOM*, we have developed an indirect observation method based on monitoring time-resolved singlet oxygen (1O2) phosphorescence kinetics. The underpinning principle of our approach relies on the fact that O2 quenches almost all triplets with near diffusion limited rate constants, resulting in the formation of 1O2, which is kinetically linked to the precursors. A kinetic model relating 1O2 phosphorescence kinetics to triplet excited states produced from isolated humic substances and in whole natural-water samples (hereafter referred to as 3CDOM*) was developed and used to determine rate constants governing 3CDOM* natural lifetimes and quenching by oxygen and 2,4,6-trimethylphenol (TMP), a common triplet probe molecule. 3CDOM* was found to exhibit smaller O2 and TMP quenching rate constants, ∼9 × 108 and ∼8 × 108 M-1 s-1, respectively, compared with model sensitizers, such as aromatic ketones. Findings from this report shed light on the fundamental photochemical properties of CDOM in organic matter isolates and whole waters and will help refine photochemical models to more accurately predict pollutant fate in the environment.

The Case Against Charge Transfer Interactions in Dissolved Organic Matter Photophysics.

The optical properties of dissolved organic matter influence chemical and biological processes in all aquatic ecosystems. Dissolved organic matter optical properties have been attributed to a charge-transfer model in which donor-acceptor complexes play a primary role. This model was evaluated by measuring the absorbance and fluorescence response of organic matter isolates to changes in solvent temperature, viscosity, and polarity, which affect the position and intensity of spectra for known donor-acceptor complexes of organic molecules. Absorbance and fluorescence spectral shape were largely unaffected by these changes, indicating that the distribution of absorbing and emitting species was unchanged. Overall, these results call into question the wide applicability of the charge-transfer model for explaining organic matter optical properties and suggest that future research should explore other models for dissolved organic matter photophysics.

Aqueous singlet oxygen reaction kinetics of furfuryl alcohol: effect of temperature, pH, and salt content.

The rate constant for the reaction between furfuryl alcohol (FFA) and singlet oxygen (1O2) in aqueous solution was measured as a function of temperature, pH and salt content employing both steady-state photolysis (ß value determination) and time-resolved singlet oxygen phosphorescence methods. The latter provided more precise and reproducible data. The reaction rate constant, krxn,FFA, had a relatively small temperature dependence, no pH dependence and showed a small increase in the presence of high salt concentrations (+19% with 1 M NaCl). A critical review of the available literature suggested that the widely used value of 1.2 × 108 M-1 s-1 is likely overestimated. Therefore, we recommend the use of 1.00 × 108 M-1 s-1 for reactions performed in low ionic strength aqueous solutions (freshwater) at 22 °C. Furthermore, corrections are provided that should be applied when working at higher or lower temperatures, and/or at high salt concentrations (seawater).

QSARs for phenols and phenolates: oxidation potential as a predictor of reaction rate constants with photochemically produced oxidants.

Quantitative structure-activity relationships (QSARs) for prediction of the reaction rate constants of phenols and phenolates with three photochemically produced oxidants, singlet oxygen, carbonate radical, and triplet excited state sensitizers/organic matter, are developed. The predictive variable is the one-electron oxidation potential (E1), which is calculated for each species using density functional theory. The reaction rate constants are obtained from the literature, and for singlet oxygen, are augmented with new experimental data. Calculated E1 values have a mean unsigned error compared to literature values of 0.04-0.06 V. For singlet oxygen, a single linear QSAR that includes both phenols and phenolates is developed that predicts experimental rate constants, on average, to within a factor of three. Predictions for only 6 out of 87 compounds are off by more than a factor of 10. A more limited data set for carbonate radical reactions with phenols and phenolates also gives a single linear QSAR with prediction of rate constant being accurate to within a factor of three. The data for the reactions of phenols with triplet state sensitizers demonstrate that two sensitizers, 2-acetonaphthone and methylene blue, most closely predict the reactivity trend of triplet excited state organic matter with phenols. Using sensitizers with stronger reduction potentials could lead to overestimation of rate constants and thus underestimation of phenolic pollutant persistence.

Photochemical and Nonphotochemical Transformations of Cysteine with Dissolved Organic Matter.

Cysteine (Cys) plays numerous key roles in the biogeochemistry of natural waters. Despite its importance, a full assessment of Cys abiotic transformation kinetics, products and pathways under environmental conditions has not been conducted. This study is a mechanistic evaluation of the photochemical and nonphotochemical (dark) transformations of Cys in solutions containing chromophoric dissolved organic matter (CDOM). The results show that Cys underwent abiotic transformations under both dark and irradiated conditions. Under dark conditions, the transformation rates of Cys were moderate and were highly pH- and temperature-dependent. Under UVA or natural sunlight irradiations, Cys transformation rates were enhanced by up to two orders of magnitude compared to rates under dark conditions. Product analysis indicated cystine and cysteine sulfinic acid were the major photooxidation products. In addition, this study provides an assessment of the contributions of singlet oxygen, hydroxyl radical, hydrogen peroxide, and triplet dissolved organic matter to the CDOM-sensitized photochemical oxidation of Cys. The results suggest that another unknown pathway was dominant in the CDOM-sensitized photodegradation of Cys, which will require further study to identify.

Photoreduction of Hg(ii) and photodemethylation of methylmercury: the key role of thiol sites on dissolved organic matter.

This study examined the kinetics of photoreduction of Hg(ii) and photodemethylation of methylmercury (MeHg(+)) attached to, or in the presence of, dissolved organic matter (DOM). Both Hg(ii) and MeHg(+) are principally bound to reduced sulfur groups associated with DOM in many freshwater systems. We propose that a direct photolysis mechanism is plausible for reduction of Hg(ii) bound to reduced sulfur groups on DOM while an indirect mechanism is supported for photodemethylation of MeHg(+) bound to DOM. UV spectra of Hg(ii) and MeHg(+) bound to thiol containing molecules demonstrate that the Hg(ii)-S bond is capable of absorbing UV-light in the solar spectrum to a much greater extent than MeHg(+)-S bonds. Experiments with chemically distinct DOM isolates suggest that concentration of DOM matters little in the photochemistry if there are enough reduced S sites present to strongly bind MeHg(+) and Hg(ii); DOM concentration does not play a prominent role in photodemethylation other than to screen light, which was demonstrated in a field experiment in the highly colored St. Louis River where photodemethylation was not observed at depths ≥ 10 cm. Experiments with thiol ligands yielded slower photodegradation rates for MeHg(+) than in experiments with DOM and thiols; rates in the presence of DOM alone were the fastest supporting an intra-DOM mechanism. Hg(ii) photoreduction rates, however, were similar in experiments with only DOM, thiols plus DOM, or only thiols suggesting a direct photolysis mechanism. Quenching experiments also support the existence of an intra-DOM photodemethylation mechanism for MeHg(+). Utilizing the difference in photodemethylation rates measured for MeHg(+) attached to DOM or thiol ligands, the binding constant for MeHg(+) attached to thiol groups on DOM was estimated to be 10(16.7).

Direct photodegradation of androstenedione and testosterone in natural sunlight: inhibition by dissolved organic matter and reduction of endocrine disrupting potential.

In surface waters, two of the most commonly observed androgenic steroid hormones are androstenedione (AD) and testosterone (T). This study compares the photodegradation of dilute (<10 µg L(-1)) aqueous solutions of AD and T in natural sunlight, and evaluates the endocrine-disrupting potential of the resulting solutions. This study also examines the effect of dissolved organic matter (DOM) on AD photodegradation. During spring and summer at Henderson, NV, USA (latitude 36.04°N), AD and T underwent direct photodegradation, with half-lives ranging from 3.7 to 10.8 h. In three model DOM solutions, AD's half-life increased by 11% to 35%. Using screening factors to eliminate DOM's inner filter effect, quantum yield calculations suggested that light screening was primarily responsible for AD's increased half-life, and that physical quenching further inhibited AD's photodegradation in two out of three DOM solutions. In vitro androgenic activity of the AD and T solutions decreased approximately as fast as AD and T were removed, suggesting that solar photodegradation reduces the risk of endocrine disruption in surface waters impacted by AD or T, subject to continuing inputs. Reduced in vitro androgenic activity appears to be related to steroid ring cleavage and the formation of highly oxidized photoproducts.

Photochemical induced changes of in vitro estrogenic activity of steroid hormones.

Steroid estrogens are endocrine disrupting contaminants frequently detected in natural waters. Because these estrogens can elicit significant biological responses in aquatic organisms, it is important to study their rates and pathways of degradation in natural waters and to identify whether the transformation products retain biological activity. Photochemical kinetics experiments were conducted under simulated solar light for the hormones 17ß-estradiol (E2), 17α-ethinylestradiol (EE2), estrone (E1), equilin (EQ), and equilenin (EQN) under direct and indirect photolysis conditions. All of these hormones were susceptible to direct photodegradation, with half-lives ranging from 40 min for E1 to about 8 h for E2 and EE2. Indirect photolysis experiments with added Suwannee River fulvic acid (SRFA) lead to faster degradation rates for E2, EE2, and EQ. Added SRFA caused slower photodegradation rates for E1 and EQN, indicating that it acts primarily as an inner filter for these analytes. The well-established yeast estrogen screen (YES) was used to measure the estrogenicity of the analytes and their photoproducts. Results of YES assay experiments show that only the direct photolysis of E1 gave estrogenic products. Lumiestrone, the major E1 direct photolysis product, was isolated and characterized. It formed in 53% yield and exhibited moderate estrogenic activity. When photolysed in the presence of perinaphthenone, a potent synthetic sensitizer, E1 degraded via an indirect photolysis pathway and did not produce lumiestrone or any other active products. These results suggest that under typical natural water conditions photochemical reactions of E2, EE2, EQ, and EQN are expected to produce inactive products while E1 will give the estrogenic product lumiestrone in moderate yield.

Aquatic photochemistry of isoflavone phytoestrogens: degradation kinetics and pathways.

Isoflavones are plant-derived chemicals that are potential endocrine disruptors. Although some recent studies have detected isoflavones in natural waters, little is known about their aquatic fates. The photochemical behaviors of the isoflavones daidzein, formononetin, biochanin A, genistein, and equol were studied under simulated solar light and natural sunlight. All of these phytoestrogens were found to be photolabile under certain conditions. Daidzein and formononetin degraded primarily by direct photolysis. Their expected near-surface summer half-lives in pH 7 water at 47° latitude are expected to be 10 and 4.6 h, respectively. Biochanin A, genistein, and equol degraded relatively slowly by direct photolysis at environmentally realistic pH values, though they showed significant degradation rate enhancements in the presence of natural organic matter (NOM). The indirect photolysis rates for these compounds scaled with NOM concentration, and NOM from microbial origin was found to be a more potent photosensitizer than NOM from terrestrial sources. Mechanistic studies were performed to determine the indirect photolysis pathways responsible for the rate enhancements. Results of these studies implicate reaction with both singlet oxygen and excited state triplet NOM. Environmental half-lives for biochanin A, genistein, and equol are expected to vary on the basis of pH as well as NOM source and concentration.

Microheterogeneous concentrations of singlet oxygen in natural organic matter isolate solutions.

The binding affinity of a hydrophobic singlet oxygen probe toward natural organic matter isolates was investigated. A linear phase-partitioning model was used to calculate partition coefficients and intramicellar concentrations of singlet oxygen several orders of magnitude larger than those reported by traditional singlet oxygen probes. From the obtained data, a kinetic model was developed to describe the microscopic environment experienced by hydrophobic compounds in natural water systems. Micellar radii and molecular weights were derived from the experimental data and evaluated. The data obtained provides additional support of a microheterogeneous environment within bulk natural solutions. The enhanced concentrations of photogenerated reactive intermediates within these microenvironments may improve understanding of hydrophobic pollutant degradation in the environment.

Microheterogeneity of singlet oxygen distributions in irradiated humic acid solutions.

Singlet oxygen (1O2) is a highly reactive species formed through solar irradiation of organic matter in environmental waters. Implicated in a range of reactions, it has proven difficult to quantify its spatial distribution in natural waters. We assessed the microheterogeneous distribution of 1O2 in irradiated solutions containing chromophoric dissolved organic matter (CDOM) by using molecular probes of varying hydrophobicity. The apparent 1O2 concentrations ([1O2]app), measured by recently developed hydrophobic trap-and-trigger chemiluminescent probe molecules, were orders of magnitude higher than those measured by the conventional hydrophilic probe molecule furfuryl alcohol. The differential [1O2]app values measured by these probes reflect a steep concentration gradient between the CDOM macromolecules and the aqueous phase. A detailed kinetic model based on the data predicts probabilistic 1O2 distributions under different solvent conditions.

Aqueous photochemistry of triclosan: formation of 2,4-dichlorophenol, 2,8-dichlorodibenzo-p-dioxin, and oligomerization products.

The photochemical fate of the antimicrobial agent triclosan is presented. Experiments performed in both natural and buffered deionized water show that triclosan rapidly photodegrades by direct photolysis (t(1/2) = 5 h, pH 8, noon summer sunlight, 45 degrees N latitude). Both 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) and 2,4-dichlorophenol (2,4-DCP) are produced. The 2,8-DCDD and 2,4-DCP also are photolabile and, thus, are intermediates. The yields for 2,8-DCDD and 2,4-DCP ranged from 3 to 12% depending on the conditions employed. When triclosan is photolyzed in the presence of Suwannee River (GA, USA) fulvic acid, a portion of the initial mass is recovered as insoluble material. Based on experiments in which the formation of insoluble material was monitored with photolysis time, it is postulated that photolysis in natural waters leads to some of the triclosan being coupled to humic matter. Triclosan also reacts rapidly with both singlet oxygen (k(rxn) = 1.07 +/- 0.03 x 10(8) M(-1) s(-1) in water of pH 10) and hydroxyl radical (k(*OH) = 5.4 +/- 0.3 X 10(9) M(-1)(s-1). Indirect photolysis pathways, however, are not expected to be important because of low steady-state concentrations of reactive oxygen species in natural waters and the efficiency of the direct photolysis of triclosan.

Photochemical fate of pharmaceuticals in the environment: cimetidine and ranitidine.

The photochemical fates of the histamine H2-receptor antagonists cimetidine and ranitidine were studied. Each of the two environmentally relevant pharmaceuticals displayed high rates of reaction with both singlet oxygen (1O2, O2(1delta(g))) and hydroxyl radical (*OH), two transient oxidants formed in sunlit natural waters. For cimetidine, the bimolecular rate constant for reaction with *OH in water is 6.5 +/- 0.5 x 10(9) M(-1) s(-1). Over the pH range 4-10, cimetidine reacts with 1O2 with bimolecular rate constants ranging from 3.3 +/- 0.3 x 10(6) M(-1) s(-1) at low pH to 2.5 +/- 0.2 x 10(8) M(-1) s(-1) in alkaline solutions. The bimolecular rate constants for ranitidine reacting with 1O2 in water ranges from 1.6 +/- 0.2 x 10(7) M(-1) s(-1) at pH 6-6.4 +/- 0.2 x 10(7) M(-1) s(-1) at pH 10. Reaction of ranitidine hydrochloride with *OH proceeds with a rate constant of 1.5 +/- 0.2 x 10(10) M(-1) s(-1). Ranitidine was also degraded in direct photolysis experiments with a half-life of 35 min under noon summertime sunlight at 45 degrees latitude, while cimetidine was shown to be resistant to direct photolysis. The results of these experiments, combined with the expected steady-state near surface concentrations of 1O2 and *OH, indicate that photooxidation mediated by 1O2 is the likely degradation pathway for cimetidine in most natural waters, and photodegradation by direct photolysis is expected to be the major pathway for ranitidine, with some degradation caused by 1O2. These predictions were verified in studies using Mississippi River water. Model compounds were analyzed by laser flash photolysis experiments to assess which functionalities within ranitidine and cimetidine are most susceptible to singlet-oxygenation and direct photolysis. The heterocyclic moieties of the pharmaceuticals were clearly implicated as the sites of reaction with 1O2, as evidenced by the high relative rate constants of the furan and imidazole models. The nitroacetamidine portion of ranitidine has been shown to be the moiety active in direct photolysis.