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.

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.

Inferring Ecosystem Function from Dissolved Organic Matter Optical Properties: A Critical Review.

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.

Multiple Roles of Dissolved Organic Matter in Advanced Oxidation Processes.

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.

A review of simulation experiment techniques used to analyze wildfire effects on water quality and supply.

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.

Nitrogen Enrichment during Soil Organic Matter Burning and Molecular Evidence of Maillard Reactions.

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.

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.

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.

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.

Foreseen Effects of Climate-Impacted Scenarios on the Photochemical Fate of Selected Cyanotoxins in Surface Freshwaters.

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.

Photodegradation of cyanotoxins in surface waters.

Cyanotoxin-producing harmful algal blooms (HABs) are a global occurrence and pose ecotoxicological threats to humans and animals alike. The presence of cyanotoxins can seriously harm or kill nearby wildlife and restrict a body of water's use as a drinking water supply and recreational site, making it imperative to fully understand their fate and transport in natural waters. Photodegradation contributes to the overall degradation of cyanotoxins in environmental systems, especially for those present in the photic zone of surface waters. This makes photochemical transformation mechanisms important factors to account for when assessing the persistence of cyanotoxins in environmental systems. This paper reviews current knowledge on the photodegradation rates and pathways of cyanotoxins that can occur over the course of HABs. Sensitized, or indirect, photolysis contributes to the degradation of all cyanotoxins addressed in this paper (anatoxins, cylindrospermopsins, domoic acids, microcystins, and nodularins), with hydroxyl radicals (•OH), excited triplet states formed from the absorption of light by dissolved organic matter (3DOM*), and photosynthetic pigment sensitized pathways being of primary interest. Direct photolysis pathways play a less significant role, but are still relevant for most of the cyanotoxins discussed in this paper.

Wildfires: Identification of a new suite of aromatic polycarboxylic acids in ash and surface water.

Ash and surface water samples collected after wildfires in four different geographical locations (California, Colorado, Kansas and Alberta) were analyzed. The ash samples were leached with deionized water, and leachates were concentrated by solid phase extraction and analyzed by liquid chromatography/time-of-flight mass spectrometry. In addition, three surface water samples and a lysimeter water sample were collected from watersheds recently affected by fire in California and Colorado, and analyzed in similar fashion. A suite of benzene polycarboxylic acids (BPCAs), with two and three carboxyl groups and their corresponding isomers were identified for the first time in both ash leachates and water samples. Also found was a pyridine carboxylic acid (PCA), 3,5-pyridine dicarboxylic acid. Furthermore, putative identifications were made for other carboxylated aromatic acids: quinolinic, naphthalenic, and benzofuranoic acid carboxylates. The wildfire ashes, a controlled wood ash, and post-fire surface water samples suggest that burned woody material, along with surface plant-material and heated o-horizon soil organic matter, contribute to both BPCAs and PCAs in runoff. This study is the first of its kind to identify this suite of aromatic acids in wildfire ash and surface water samples. These data make an important contribution to the nature of dissolved organic matter from wildfire and are useful to better understand the impact of wildfire on water quality and drinking water sources.

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.

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.

Some issues limiting photo(cata)lysis application in water pollutant control: A critical review from chemistry perspectives.

For decades, photolysis and photocatalysis have been touted as promising environment-benign and robust technologies to degrade refractory pollutants from water. However, extensive, large-scale engineering applications remain limited now. To facilitate the technology transfer process, earlier reviews have advocated to developing more cost-effective and innocuous materials, maximizing efficiency of photon usage, and optimizing photoreactor systems, mostly from material and reactor improvement perspectives. However, there are also some fundamental yet critical chemistry issues in photo(cata)lysis processes demanding more in-depth understanding and more careful consideration. Hence, this review summarizes some of these challenges. Of them, the first and paramount issue is the interference of coexisting compounds, including dissolved organic matter, anions, cations, and spiked additives. Secondly, considerable concerns are pointed to the formation of undesirable reaction by-products, such as halogenated, nitrogenous, and sulfur-containing compounds, which might increase instead of reduce toxicity of water if inadequate fluence and catalyst/additive are supplied due to time and cost constraints. Lastly, a critical issue lies in the uncertainty of current approaches used for identifying and quantifying radicals, especially when multiple radicals coexist together under changing and interconvertible conditions. The review hence highlights the needs to better understand these fundamental chemistry issues and meanwhile calls for more delicate design of experiments in future studies to overcome these barriers.

Photolysis and photocatalysis of haloacetic acids in water: A review of kinetics, influencing factors, products, pathways, and mechanisms.

Haloacetic acids (HAAs) are a group of pollutants ubiquitous in natural environment and anthropogenic systems, and therefore in need of control. Photolysis and photocatalysis techniques via ultraviolet (UV)-based technologies have held promise for decades in degrading organic molecules in water, but their capacities in removing HAAs remain to be explored. To better understand the trends in the existing literature and to identify the knowledge gaps that may merit further exploration, this review compares the HAAs photodegradation kinetics, influencing factors, reaction products, pathways, and mechanisms for a variety of UV technologies. The selected UV processes are classified into three types: UV-only photolysis, photooxidation, and photoreduction. Overall, although trends vary significantly depending upon many factors, the photo-susceptibility of HAAs always increases with rising molecular weight of substituted halogen atom(s), with those chlorinated HAAs being the most refractory species. Notably, while many processes proved hydroxyl radical (OH) as the forcing driver, the patterns of kinetics among HAAs were not consistent among processes, suggesting that OH was not the only driver. Compared to earlier studies focusing on specific technologies to treat numerous contaminants through a material perspective, this review commits to understanding the commonalities and differences among multiple UV-based technologies in treating only one group of compound mainly via a chemistry viewpoint.

Molecular Identification of Water-Extractable Organic Carbon from Thermally Heated Soils: C-13 NMR and Accurate Mass Analyses Find Benzene and Pyridine Carboxylic Acids.

To simulate the effects of wildfire on the combustion process in soils and their potential to leach organic compounds into streams and groundwater, mineral soil samples were heated at temperatures of 150-550 °C. Then, the soils were leached with deionized water, filtered, and analyzed for dissolved organic carbon. The water extract was concentrated by both XAD-8 and XAD-4 resins and analyzed by C-13 nuclear magnetic resonance and liquid chromatography time-of-flight mass spectrometry. Approximately 15-20% of the water-extractable organic carbon was identified as benzene dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acid isomers, commonly called BPCAs. Also identified were isomers of pyridine dicarboxylic acids and tricarboxylic acids (PCAs). The conversion of soil organic carbon to BPCAs occurs at 250 °C and reaches a maximum between 350 and 450 °C. At higher temperatures (>450 °C), the BPCA concentrations decrease, suggesting decarboxylation and conversion to carbon dioxide and water. This is the first report of BPCAs and PCAs in water-extractable organic carbon from thermally altered soil and suggest that these compounds are possible candidates for further water-quality studies in watersheds affected by wildfire. Finally, BPCAs and PCAs could contribute to the black carbon and nitrogen in seawater and are worthy of future investigation.