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 (CO), 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 CO. Results suggest that CO formation occurs in a biphasic kinetic system, with fast production occurring within the first 3 h, followed by slower production thereafter.

Evaluating the Use of UV Absorbance for the Differentiation of Humified From Non-Humified Materials.

Background: Products containing humic acids (HA) and fulvic acids (FA) have significant commercial potential; however, unknown to the consumer, some products may be mislabeled or contain adulterants. The prevalence of mislabeling and adulterants is found primarily in FA products. Using UV-Vis spectroscopy to differentiate between real and fake FA products is practical and desirable.

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 DOM* and PPCPs in various water bodies, this study defines a reaction rate coefficient ( [Formula: see text] ) to describe the reaction between DOM* 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.

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 (Φ) as a function of the apparent molecular weight (AMW). Size-based fractions of each isolate were collected and irradiated to measure singlet oxygen (O) quantum yield (Φ).

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.

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.

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.

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.

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 (O), excited triplet state DOM (DOM*), 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).

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.

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 (PM) in the aqueous phase. PM was collected during a winter, a spring, and a summer campaign in urban and rural settings in Colorado and extracted into water.

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.

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.

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.

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.

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.

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.

Molecular Transformation of Crude Oil Contaminated Soil after Bioelectrochemical Degradation Revealed by FT-ICR Mass Spectrometry.

Bioremediation is a low-cost approach for crude oil spill remediation, but it is often limited by electron acceptor availability. In addition, the biodegradation products of crude oil contaminants are complex, and transformation pathways are difficult to decipher. This study demonstrates that bioelectrochemical systems (BESs) can be effective in crude oil degradation by integrating biological and electrochemical pathways, and more importantly, it provides the first understanding on the daughter products of bioelectrochemical hydrocarbon degradation.

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.

Methodology for selection of optical parameters as wastewater effluent organic matter surrogates.

Absorbance- and fluorescence-based optical parameters are commonly used as surrogates in engineered systems, but there is no systematic approach for selecting robust parameters. This study develops a methodology that is applied to a case study of differentiating wastewater effluent organic matter from naturally-derived organic matter. The methodology defines criteria to identify optical parameters that could detect statistically significant compositional differences in organic matter, independent of organic matter concentration, and measure fluorescence-based parameters with low susceptibility to inner filter effects.

Wildfires Alter Forest Watersheds and Threaten Drinking Water Quality.

Wildfires are a natural part of most forest ecosystems, but due to changing climatic and environmental conditions, they have become larger, more severe, and potentially more damaging. Forested watersheds vulnerable to wildfire serve as drinking water supplies for many urban and rural communities. The highly variable nature of wildfire behavior combined with spatially complex patterns in vegetation, landscape, and hydrologic factors create uncertainty surrounding the postfire effects on water supplies.