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.

Meta-Analysis of Optical Surrogates for the Characterization of Dissolved Organic Matter.

Optical surrogates, derived from absorbance and fluorescence spectra, are widely used to infer dissolved organic matter (DOM) composition (molecular weight, aromaticity) and genesis (autochthonous vs allochthonous). Despite the broad adoption of optical surrogates, several limitations exist, such as context- and sample-specific factors. These limitations create uncertainty about how compositional interpretations based on optical surrogates are generalized across contexts, specifically if there is duplicative or contradictory information in those interpretations. To explore these limitations, we performed a meta-analysis of optical surrogates for DOM from diverse sources, both from natural systems and after water treatment processes (n = 762). Prior to analysis, data were screened using a newly developed, standardized methodology that applies systematic quality control criteria before reporting surrogates. There was substantial overlap in surrogate values from natural and treated samples, suggesting that the gradients governing the surrogate variability can be generated in both contexts. This overlap provides justification for using optical surrogates originally developed in the context of natural systems to describe DOM changes in engineered systems, although the interpretations may change. Absorbance-based surrogates that describe the amount of spectral tailing (e.g., E2:E3 and S275-295) had a high frequency of strong correlations with one another but not to specific absorbance (SUVA254) or absorbance slope ratio (SR). The fluorescence index (FI) and biological index (ß/α) were strongly correlated with one another and to the peak emission wavelength but not to the humification index (HIX). Although SUVA254 and FI have both been correlated to DOM aromaticity in prior research, there was a lack of reciprocity between these optical surrogates across this data set. Additionally, there were patterns of deviations in the wastewater subset, suggesting that effluent organic matter may not follow conventional interpretations, urging caution in the use of optical surrogates to track DOM in water reuse applications. Finally, the meta-analysis highlights that three aspects should be captured when optical spectra are used for DOM interpretation: specific absorbance, absorbance tailing, and the extent of red-shifted fluorescence. We recommend that SUVA254, E2:E3, and FI or ß/α be prioritized in future DOM studies to capture these aspects, respectively.

Evaluating the pH-dependence of DOM absorbance, fluorescence, and photochemical production of singlet oxygen.

The protonation state of dissolved organic matter (DOM) impacts its structure and function in natural and engineered environmental systems, including DOM's ability to absorb light and form photochemically produced reactive intermediates (PPRI). However, the impacts of pH on DOM optical properties and PPRI formation have largely been evaluated separately, with less information being available on their interrelationship as a function of pH for the same set of samples. It is also unclear whether the impact of pH on optical spectra and associated optical surrogates for molecular size (e.g., E2 : E3) of DOM isolates is representative of the behavior of whole water samples. To address these knowledge gaps, spectral pH titrations were performed for seven humic substance and natural organic matter isolates, three whole water samples, and three model compounds. Comparison of the fractional and differential absorption and fluorescence spectra between DOM isolates, whole water samples, and model compounds revealed similar spectral features between all samples. The results show that spectral features observed for DOM isolates also occur for whole water samples, which suggests that there is overlap in the types of chromophores present in DOM isolates and whole waters. Although results from model compounds overlapped with DOM, especially in the ultraviolet region of the spectrum, no model compound replicated DOM's pH dependence perfectly. By measuring apparent quantum yields of singlet oxygen (ΦΔ), we show that aquatic DOM isolates exhibit a different pH-dependence (ΦΔ âˆ pH-1) than soil-derived humic acid isolates (ΦΔ âˆ pH). For aquatic DOM isolates, ΦΔ values measured at different pH were not correlated to apparent fluorescence quantum yields (Φf), suggesting that pH impacts singlet and triplet excited state DOM dynamics in different ways. In contrast, the proportional relationship between Φf and ΦΔ with increasing pH for soil humic acid isolates suggests that pH impacts singlet and triplet excited DOM in these samples in a similar fashion.

Evaluating the Microheterogeneous Distribution of Photochemically Generated Singlet Oxygen Using Furfuryl Amine.

Singlet oxygen (1O2) is an important reactive species in natural waters produced during photolysis of dissolved organic matter (DOM). Prior studies have demonstrated that 1O2 exhibits a microheterogeneous distribution, with [1O2] in the interior of DOM macromolecules ∼30 to 1000-fold greater than in bulk solution. The [1O2] profile for DOM-containing solutions has been determined mainly by the use of hydrophobic probes, which are not commercially available. In this study, we employed a dual-probe method combining the widely used hydrophilic 1O2 probe furfuryl alcohol (FFA) and its structural analogue furfuryl amine (FFAm). FFAm exists mainly as a cation at pH <9 and was therefore hypothesized to have an enhanced local concentration in the near-DOM phase, whereas FFA will be distributed homogeneously. The probe pair was used to quantify apparent [1O2] in DOM samples from different isolation procedures (humic acid, fulvic acid, reverse osmosis) and diverse origins (aquatic and terrestrial) as a function of pH and ionic strength, and all samples studied exhibited enhanced reactivity of FFAm relative to FFA, especially at pH 7 and 8. To quantify the spatial distribution of [1O2], we combined electrostatic models with Latch and McNeill's three-phase distribution model. Modeling results for Suwannee River humic acid (SRHA) yield a surface [1O2] of ∼60 pM, which is ∼96-fold higher than the aqueous-phase [1O2] measured with FFA. This value is in agreement with prior reports that determined 1-3 orders of magnitude higher [1O2] in the DOM phase compared to bulk solution. Overall, this work expands the knowledge base of DOM microheterogeneous photochemistry by showing that diverse DOM isolates exhibit this phenomenon. In addition, the dual-probe approach and electrostatic modeling offer a new way to gain mechanistic insight into the spatial distribution of 1O2 and potentially other photochemically produced reactive intermediates.

Reactivity of Dissolved Organic Matter with the Hydrated Electron: Implications for Treatment of Chemical Contaminants in Water with Advanced Reduction Processes.

Advanced reduction processes (ARP) have garnered increasing attention for the treatment of recalcitrant chemical contaminants, most notably per- and polyfluoroalkyl substances (PFAS). However, the impact of dissolved organic matter (DOM) on the availability of the hydrated electron (eaq-), the key reactive species formed in ARP, is not completely understood. Using electron pulse radiolysis and transient absorption spectroscopy, we measured bimolecular reaction rates constant for eaq- reaction with eight aquatic and terrestrial humic substance and natural organic matter isolates ( kDOM,eaq-), with the resulting values ranging from (0.51 ± 0.01) to (2.11 ± 0.04) × 108 MC-1 s-1. kDOM,eaq- measurements at varying temperature, pH, and ionic strength indicate that activation energies for diverse DOM isolates are ≈18 kJ mol-1 and that kDOM,eaq- could be expected to vary by less than a factor of 1.5 between pH 5 and 9 or from an ionic strength of 0.02 to 0.12 M. kDOM,eaq- exhibited a significant, positive correlation to % carbonyl carbon for the isolates studied, but relationships to other DOM physicochemical properties were surprisingly more scattered. A 24 h UV/sulfite experiment employing chloroacetate as an eaq- probe revealed that continued eaq- exposure abates DOM chromophores and eaq- scavenging capacity over a several hour time scale. Overall, these results indicate that DOM is an important eaq- scavenger that will reduce the rate of target contaminant degradation in ARP. These impacts are likely greater in waste streams like membrane concentrates, spent ion exchange resins, or regeneration brines that have elevated DOM concentrations.

Fluorescence Quenching of Humic Substances and Natural Organic Matter by Nitroxide Free Radicals.

Fluorescence spectroscopy is one of the most frequently used techniques for studying dissolved organic matter (DOM) in natural and engineered systems. However, the spatial distribution and fluorophores, including local and interacting states, within DOM's larger structure remains poorly understood. In this study, we used two nitroxide fluorescence quenchers to evaluate the chemical and spatial heterogeneity of DOM fluorophores. Several results from quenching experiments with cationic 4-amino-TEMPO (tempamine), including downward-curving Stern-Volmer plots and spectral dependent quenching, show that multiple emitting species contribute to the observed emission even at a single excitation wavelength. Furthermore, for DOM isolates of diverse geographic origins (soil vs aquatic) and isolation procedures (reverse osmosis vs humic substances), the maximum extent of quenching occurs on the red edge of the emission spectra. For soil humic substance isolates, the spectral dependent quenching was significant enough to affect a blue shift in the average emission wavelength. The same soil humic substance isolates whose emission spectra were blue shifted by tempamine quenching were also blue shifted by decreasing solution pH and decreasing solvent polarity, which suggests a role for anionic fluorophores (e.g., hydroxybenzoic acids) in long wavelength fluorescence. Finally, curvature in Stern-Volmer plots indicate that between 10 and 50% of emitting species detected by steady-state fluorescence are inaccessible to quenching by tempamine, suggesting that this fraction of fluorophores may be inaccessible to water solvent. Results from this study provide an assessment of the spatial distribution of fluorophores within DOM and help to reconcile prior studies on the role of solvent polarity and pH on DOM fluorescence.

Quantifying Hydrated Electron Transformation Kinetics in UV-Advanced Reduction Processes Using the Re-,UV Method.

Ultraviolet advanced reduction processes (UV-ARP) have garnered significant attention recently for the degradation of several hard to treat contaminants, including recalcitrant per- and polyfluoroalkyl substances (PFAS). The rate of contaminant degradation in UV-ARP is directly related to the available hydrated electron concentration ([eaq-]). However, reports of [eaq-] and other parameters typically used to characterize photochemical systems are not widely reported in the UV-ARP literature. Deploying monochloroacetate as a probe compound, we developed a method (Re-,UV) to quantify the time-based hydrated electron concentration ([eaq]t) available for contaminant degradation relative to inputted UV fluence. Measured [eaq]t was then used to understand the impact of eaq- rate of formation and scavenging capacity on the degradation of two contaminants─nitrate and perfluorooctane sulfonate (PFOS)─in four source waters with varying background water quality. The results show that the long-term treatability of PFOS by UV-ARP is not significantly impacted by the initial eaq- scavenging conditions but rather is influenced by the presence of eaq- scavengers like dissolved organic carbon and bicarbonate. Lastly, using [eaq]t, degradation of nitrate and PFOS was modeled in the source waters. We demonstrate that the Re-,UV method provides an effective tool to assess UV-ARP treatment performance in a variety of source waters.

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.

Critical Review of UV-Advanced Reduction Processes for the Treatment of Chemical Contaminants in Water.

UV-advanced reduction processes (UV-ARP) are an advanced water treatment technology characterized by the reductive transformation of chemical contaminants. Contaminant abatement in UV-ARP is most often accomplished through reaction with hydrated electrons (eaq -) produced from UV photolysis of chemical sensitizers (e.g., sulfite). In this Review, we evaluate the photochemical kinetics, substrate scope, and optimization of UV-ARP. We find that quantities typically reported in photochemical studies of natural and engineered systems are under-reported in the UV-ARP literature, especially the formation rates, scavenging capacities, and concentrations of key reactive species like eaq -. The absence of these quantities has made it difficult to fully evaluate the impact of operating conditions and the role of water matrix components on the efficiencies of UV-ARP. The UV-ARP substrate scope is weighted heavily toward contaminant classes that are resistant to degradation by advanced oxidation processes, like oxyanions and per- and polyfluoroalkyl substances. Some studies have sought to optimize the UV-ARP treatment of these contaminants; however, a thorough evaluation of the impact of water matrix components like dissolved organic matter on these optimization strategies is needed. Overall, the data compilation, analysis, and research recommendations provided in this Review will assist the UV-ARP research community in future efforts toward optimizing UV-ARP systems, modeling the eaq --based chemical transformation kinetics, and developing new UV-ARP systems.

Pilot-scale field demonstration of a hybrid nanofiltration and UV-sulfite treatment train for groundwater contaminated by per- and polyfluoroalkyl substances (PFASs).

Previous laboratory scale studies indicate nanofiltration (NF) and UV-sulfite photochemical treatments as promising technologies for the removal and destruction, respectively, of per- and polyfluoroalkyl substances (PFASs) from contaminated water. This study reports on a field demonstration of a pilot-scale hybrid NF and UV-sulfite treatment train for the remediation of 12 PFASs detected in groundwater impacted by aqueous film-forming foam (AFFF) at a U.S. Department of Defense installation. For most of the detected PFASs, NF rejection was consistently ≥ 95% over a 30-day field trial when operating at 90% total permeate recovery. Rejection of short-chain perfluorosulfonic acids (PFSAs) by NF decreased when recoveries increased from 90 to 97%; tests with a reverse osmosis (RO) membrane showed ≥ 99% rejection of all PFASs regardless of increasing recovery. UV treatment of the NF reject following 90% permeate recovery resulted in variable destruction of individual PFASs, with rates also being dependent on pH and the identity and concentration of UV photosensitizer. Rates of perfluorocarboxylic acid (PFCA) degradation were greater than those measured for PFSAs and perfluoroalkyl acid (PFAA) precursors and were independent of perfluoroalkyl chain length. In contrast, rates of PFSA degradation increased with increasing chain length. Consistent levels of PFAS degradation by UV-sulfite were observed during a 30-day demonstration experiment in NF reject water amended with 10 mM sulfite and adjusted to pH 11.2. Collectively, > 75% of the detected PFAS mass in the NF reject was destroyed after 4 h of UV treatment, increasing to > 90% after 8 h of treatment. An analysis of electrical energy inputs for the hybrid NF/UV-sulfite treatment train showed energy per order magnitude (EE/O) requirements ranging from ≤ 13.1 kWh/m3 for PFCAs and 14.1 kWh/m3 for PFOS to values > 100 kWh/m3 for more recalcitrant short-chain PFSA analogues. The UV reactor and water-cooling system were the major contributors to overall energy requirements and represent the greatest opportunities for improving efficiency of the technology.

Relationships between the Physicochemical Properties of Dissolved Organic Matter and Its Reaction with Sodium Borohydride.

The reaction of dissolved organic matter (DOM) with sodium borohydride has been used to understand the geographic origin of DOM and investigate the photophysical model underlying DOM's optical properties. However, the physicochemical properties of DOM (e.g., molecular size and charge) that influence the kinetics and ultimate reducibility of DOM by borohydride remain poorly characterized. Herein, we studied the kinetics of DOM-borohydride reactions by recording absorbance and fluorescence spectra at a high temporal frequency (every ∼10 min for 24 h) for a diverse set of DOM isolates of aquatic and soil origin. The reducibility of DOM by sodium borohydride (as judged by relative removal of initial absorbance) varied appreciably among the DOM samples studied, with soil humic substances being less reducible than aquatic humic substances and natural organic matter. While statistically significant correlations were found between the reducibility of DOM and descriptors of molecular size, these descriptors were not able to differentiate the reducibility of soil versus aquatic DOM isolates that had similar bulk properties. Thus, it appears that the extent of absorbance removal by borohydride is largely driven by the origin of the humic substance isolate (aquatic vs soil) instead of molecular size or charge. Borohydride reduction resulted in increased fluorescence emission across UV and visible excitation wavelengths. However, the enhanced emission at visible excitation decreased over a time period of hours to days, suggesting that reduction of an important subset of DOM chromophores is reversible. This reversibility in fluorescence emission is consistent with the small role of quinones in the absorbance of DOM but suggests a more important role for quinone-containing charge-transfer contacts in the fluorescence of DOM, particularly at visible excitation wavelengths.

Computational Assessment of the Three-Dimensional Configuration of Dissolved Organic Matter Chromophores and Influence on Absorption Spectra.

The three-dimensional configuration of dissolved organic matter (DOM) is an important factor in determining the role of DOM in natural and engineered systems, yet there is still considerable uncertainty regarding the formation and potential stability of molecular aggregates within DOM. In this paper, we describe a computational assessment of the three-dimensional configuration of DOM. Specifically, we were interested in evaluating the hypothesis that DOM forms thermodynamically stable molecular aggregates that as a result were potentially shielded from water solvent molecules. Molecular dynamics simulations of DOM model compounds carefully selected based on ultrahigh-resolution mass spectrometry data revealed that, while DOM does indeed form molecular aggregates, the large majority of molecules (especially, O-atom bearing molecules) are solvent accessible. Additionally, these computations revealed that molecular aggregates are weak and dissociate when placed in organic solvents (tetrahydrofuran, methyl tert-butyl ether). Time-dependent density functional theory calculations demonstrated long-wavelength absorbance for both model DOM chromophores and their molecular aggregates. This study has important implications for determining the origin of DOM optical properties and for enhancing our collective understanding of DOM three-dimensional structures.

Emerging investigator series: critical review of photophysical models for the optical and photochemical properties of dissolved organic matter.

Optical measurements (absorbance and fluorescence) are widely used to track dissolved organic matter (DOM) quantity and quality in natural and engineered systems. Despite many decades of research on the optical properties of DOM, there is a lack of understanding with regards to the underlying photophysical model that is the basis for these optical properties. This review both summarizes advances to date on the photophysical properties of DOM and seeks to critically evaluate the photophysical models for DOM optical properties. Recent studies have refined the quantitative understanding of DOM photophysical properties such as excited state lifetimes and energies, rates of different photophysical processes, and quantum yields. Considering fundamental models, more clarity is needed on whether DOM photophysical processes are due to a superposition of non-interacting components (superposition model), or whether a portion of optical signals can be ascribed to electronically interacting moieties, for example in the form of electron donor-acceptor complexes (charge transfer model). Multiple studies over more than two decades have provided evidence for the charge transfer model. Questions have been raised, however, about the broad applicability of the charge transfer model. The charge transfer and superposition model are critically reviewed in light of this current research. Recommendations are given for future studies to help clarify the accuracy of these competing photophysical models.

Use of optical properties for evaluating the presence of pyrogenic organic matter in thermally altered soil leachates.

The increased frequency and severity of wildfires in forested watersheds has the potential to significantly impact the quantity and quality of water extractable organic matter (WEOM) exported from these ecosystems. This study examined the optical properties of WEOM from laboratory heated soil in order to understand physicochemical changes occurring in the organic matter as a result of heating, as well as test the usefulness of optical parameters for assessing the presence of pyrogenic organic matter. WEOM absorbance and fluorescence spectral shape and intensity varied systematically as a function of soil heating temperature. Notably, absorbance and fluorescence intensity, specific ultraviolet absorbance, apparent fluorescence quantum yield, specific fluorescence emission intensity, and maximum fluorescence emission wavelength exhibited consistent changes with heating temperature and indicated that WEOM in heated soil leachates was lower in molecular weight and more aromatic than in unheated samples. The lower molecular weight in heated soil WEOM was corroborated with size-exclusion chromatography measurements. This work increases the understanding of the molecular changes occurring in WEOM as a result of wildfire and indicates that optical measurements (i.e., absorbance and fluorescence) could be used for watershed monitoring of post-fire pyrogenic organic matter.

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.

Ozone and chlorine reactions with dissolved organic matter - Assessment of oxidant-reactive moieties by optical measurements and the electron donating capacities.

Oxidation processes are impacted by the type, concentration and reactivity of the dissolved organic matter (DOM). In this study, the reactions between various types of DOM (Suwannee River fulvic acid (SRFA), Nordic Reservoir NOM (NNOM) and Pony Lake fulvic acid (PLFA)) and two oxidants (ozone and chlorine) were studied in the pH range 2-9 by using a combination of optical measurements and electron donating capacities. The relationships between residual electron donating capacity (EDC) and residual absorbance showed a strong pH dependence for the ozone-DOM reactions with phenolic functional groups being the main reacting moieties. Relative EDC and absorbance abatements (UV254 or UV280) were similar at pH 2. At pH 7 or 9, the relative abatement of EDC was more pronounced than for absorbance, which could be explained by the formation of UV-absorbing products such as benzoquinone from the transformation of phenolic moieties. An increase in fluorescence abatement with increasing pH was also observed during ozonation. The increase in fluorescence quantum yields could not be attributed to formation of benzoquinone, but related to a faster abatement of phenolic moieties relative to fluorophores with low ozone reactivity. The overall •OH yields as a result of DOM-induced ozone consumption increased significantly with increasing pH, which could be related to the higher reactivity of phenolic moieties at higher pH. The •OH yields for SRFA and PLFA were proportional to the phenolic contents, whereas for NNOM, the •OH yield was about 30% higher. During chlorination of DOM at pH 7 an efficient relative EDC abatement was observed whereas the relative absorbance abatement was much less pronounced. This is due to the formation of chlorophenolic moieties, which exert a significant absorbance, and partly lose their electron donating capacity. Pre-ozonation of SRFA leads to a decrease of chloroform and haloacetic acid formation, however, only after a threshold of > ∼50% abatement of the EDC and under conditions which are not precursor limited. The decrease in chloroform and haloacetic acid formation after the threshold EDC abatement was proportional to the relative residual EDC.

Temperature Dependence of Dissolved Organic Matter Fluorescence.

The temperature dependence of organic matter fluorescence apparent quantum yields (Φf) was measured for a diverse set of organic matter isolates (i.e., marine aquatic, microbial aquatic, terrestrial aquatic, and soil) in aqueous solution and for whole water samples to determine apparent activation energies ( Ea) for radiationless decay processes of the excited singlet state. Ea was calculated from temperature dependent Φf data obtained by steady-state methods using a simplified photophysical model and the Arrhenius equation. All aquatic-derived isolates, all whole water samples, and one soil-derived fulvic acid isolate exhibited temperature dependent Φf values, with Ea ranging from 5.4 to 8.4 kJ mol-1 at an excitation wavelength of 350 nm. Conversely, soil humic acid isolates exhibited little or no temperature dependence in Φf. Ea varied with excitation wavelength in most cases, typically exhibiting a decrease between 350 and 500 nm. The narrow range of Ea values observed for these samples when compared to literature Ea values for model fluorophores (∼5-30 kJ mol-1) points to a similar photophysical mechanism for singlet excited states nonradiative inactivation across organic matter isolates of diverse source and character. In addition, this approach to temperature dependent fluorescence analysis provides a fundamental, physical basis, in contrast to existing empirical relationships, for correcting online fluorescence sensors for temperature effects.

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.

Low levels of iron enhance UV/H2O2 efficiency at neutral pH.

While the presence of iron is generally not seen as favorable for UV-based treatment systems due to lamp fouling and decreased UV transmittance, we show that low levels of iron can lead to improvements in the abatement of chemicals in the UV-hydrogen peroxide advanced oxidation process. The oxidation potential of an iron-assisted UV/H2O2 (UV254 + H2O2 + iron) process was evaluated at neutral pH using iron levels below USEPA secondary drinking water standards (<0.3 mg/L). Para-chlorobenzoic acid (pCBA) was used as a hydroxyl radical (HO) probe to quantify HO steady state concentrations. Compounds degraded by different mechanisms including, carbamazepine (CBZ, HO oxidation) and N-nitrosodimethylamine (NDMA, direct photolysis), were used to investigate the effect of iron on compound degradation for UV/H2O2 systems. The effects of iron species (Fe2+ and Fe3+), iron concentration (0-0.3 mg/L), H2O2 concentration (0-10 mg/L) and background water matrix (low-carbon tap (LCT) and well water) on HO production and compound removal were examined. Iron-assisted UV/H2O2 efficiency was most influenced by the target chemical and the water matrix. Added iron to UV/H2O2 was shown to increase the steady-state HO concentration by approximately 25% in all well water scenarios. While CBZ removal was unchanged by iron addition, 0.3 mg/L iron improved NDMA removal rates in both LCT and well water matrices by 15.1% and 4.6% respectively. Furthermore, the combination of UV/Fe without H2O2 was also shown to enhance NDMA removal when compared to UV photolysis alone indicating the presence of degradation pathways other than HO oxidation.