Download or read book Spatiotemporal Variability in Dissolved Organic Matter Composition and Its Relationship to Photochemical Reactivity written by Stephanie Berg (Ph.D.) and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Dissolved organic matter (DOM) is a ubiquitous group of biologically derived organic molecules found in all natural waters. DOM makes up a substantial amount of the carbon stored in surface waters, and its original sources include allochthonous, or terrestrial, inputs as well as autochthonous, or aquatic, inputs. It is primarily made of up small (i.e.,

Download or read book The Influence of Dissolved Organic Matter Composition on Its Reactivity in Natural and Engineered Systems written by Reid Milstead and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Dissolved organic matter (DOM) is a complex heterogeneous mixture of organic compounds that is found in all water systems. DOM is derived from both terrestrial and microbial sources. The composition of DOM can vary greatly depending on a number of variables, including time of year, surrounding groundcover type, and water column depth. The characterization of DOM composition is increasingly performed using high-resolution mass spectrometry, although different instrumentation and techniques may yield different results. Importantly, DOM plays a key role in a number of chemical processes in both natural and engineered systems, such as the generation of carbon dioxide (CO2) from surface waters, the degradation of aquatic contaminants, and the formation of disinfection byproducts (DBPs) during drinking water treatment. The composition of DOM determines its reactivity in all of these processes. Using both bulk and high-resolution analytical techniques, the photooxidation of DOM can be explored. DOM compounds that are more oxidized and aromatic tend to be associated with the consumption of oxygen and the production of CO2. Bulk scale measurements show that DOM becomes less aromatic and lower in molecular weight as a result of partial photooxidation. High-resolution mass spectrometry also provides evidence of oxygen addition and the loss of CO2 from DOM during irradiation experiments. However, the chemical formulas that are most photolabile vary depending on the initial composition of DOM. Using light exposure experiments the kinetics of degradation of four contaminants were quantified for a large set of diverse waters. Using this information, we evaluated the relationships between indirect photolysis rate constants and the formation of photochemically produced reactive intermediates (PPRI) using linear regression analysis. Additionally, quencher experiments were performed to identify the PPRI associated with the degradation of each contaminant in all waters. Triplet state DOM (3DOM) and singlet oxygen (1O2) were identified as critical for atorvastatin, carbamazepine, and sulfadiazine, while hydroxyl radical (•OH) is important for benzotriazole. Our results suggest that quenching experiments should be used with caution due to the non-targeted nature of quenching compounds and the interconnection of PPRI. All of these factors result in probe compounds possibly overstating the importance of PPRI in the indirect photolysis of common contaminants. The characterization of DOM in drinking waters reveals a high degree of variability in DOM composition and reactivity with chlorine, particularly in groundwater samples. Despite the variability in DOM composition, novel DBPs with up to three halogen substituents are compositionally similar among all waters. These novel DBPs are positively correlated with trihalomethane and, to a lesser extent, the formation of haloacetonitriles. This suggests that some low molecular weight DBPs and novel DBPs detected via high-resolution mass spectrometry share similar aromatic precursors, providing evidence that low molecular weight DBPs are useful proxies for the formation of unknown, unidentified high molecular weight DBPs. Compared to Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS), Orbitrap MS yields significantly fewer formula matches and appears to have a bias towards sulfur-containing formulas and against nitrogen-containing formulas. Additionally, the choice of calibration method is particularly important for the less powerful Orbitrap MS. The matched formulas yielded from Orbitrap MS tend to be more oxidized and less highly saturated than those yielded by FT-ICR MS. Despite these differences, the formulas produced by both instruments tend to yield similar relative differences between samples, suggesting that Orbitrap MS is an acceptable replacement for FT-ICR MS in some cases.

Download or read book The Influence of Dissolved Organic Matter Composition on Its Reactivity in Natural and Engineered Systems written by Reid Milstead and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Dissolved organic matter (DOM) is a complex heterogeneous mixture of organic compounds that is found in all water systems. DOM is derived from both terrestrial and microbial sources. The composition of DOM can vary greatly depending on a number of variables, including time of year, surrounding groundcover type, and water column depth. The characterization of DOM composition is increasingly performed using high-resolution mass spectrometry, although different instrumentation and techniques may yield different results. Importantly, DOM plays a key role in a number of chemical processes in both natural and engineered systems, such as the generation of carbon dioxide (CO2) from surface waters, the degradation of aquatic contaminants, and the formation of disinfection byproducts (DBPs) during drinking water treatment. The composition of DOM determines its reactivity in all of these processes. Using both bulk and high-resolution analytical techniques, the photooxidation of DOM can be explored. DOM compounds that are more oxidized and aromatic tend to be associated with the consumption of oxygen and the production of CO2. Bulk scale measurements show that DOM becomes less aromatic and lower in molecular weight as a result of partial photooxidation. High-resolution mass spectrometry also provides evidence of oxygen addition and the loss of CO2 from DOM during irradiation experiments. However, the chemical formulas that are most photolabile vary depending on the initial composition of DOM. Using light exposure experiments the kinetics of degradation of four contaminants were quantified for a large set of diverse waters. Using this information, we evaluated the relationships between indirect photolysis rate constants and the formation of photochemically produced reactive intermediates (PPRI) using linear regression analysis. Additionally, quencher experiments were performed to identify the PPRI associated with the degradation of each contaminant in all waters. Triplet state DOM (3DOM) and singlet oxygen (1O2) were identified as critical for atorvastatin, carbamazepine, and sulfadiazine, while hydroxyl radical (•OH) is important for benzotriazole. Our results suggest that quenching experiments should be used with caution due to the non-targeted nature of quenching compounds and the interconnection of PPRI. All of these factors result in probe compounds possibly overstating the importance of PPRI in the indirect photolysis of common contaminants. The characterization of DOM in drinking waters reveals a high degree of variability in DOM composition and reactivity with chlorine, particularly in groundwater samples. Despite the variability in DOM composition, novel DBPs with up to three halogen substituents are compositionally similar among all waters. These novel DBPs are positively correlated with trihalomethane and, to a lesser extent, the formation of haloacetonitriles. This suggests that some low molecular weight DBPs and novel DBPs detected via high-resolution mass spectrometry share similar aromatic precursors, providing evidence that low molecular weight DBPs are useful proxies for the formation of unknown, unidentified high molecular weight DBPs. Compared to Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS), Orbitrap MS yields significantly fewer formula matches and appears to have a bias towards sulfur-containing formulas and against nitrogen-containing formulas. Additionally, the choice of calibration method is particularly important for the less powerful Orbitrap MS. The matched formulas yielded from Orbitrap MS tend to be more oxidized and less highly saturated than those yielded by FT-ICR MS. Despite these differences, the formulas produced by both instruments tend to yield similar relative differences between samples, suggesting that Orbitrap MS is an acceptable replacement for FT-ICR MS in some cases.

Download or read book Photochemical Reactivity of Dissolved Organic Matter in the Delaware Estuary written by Emily M White and published by . This book was released on 2007 with total page 474 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Relating Dissolved Organic Matter Composition and Photochemistry with High Resolution Mass Spectrometry written by Andrew Chapin Maizel and published by . This book was released on 2017 with total page 301 pages. Available in PDF, EPUB and Kindle. Book excerpt: The irradiation of dissolved organic matter (DOM) produces reactive intermediates, such as excited triplet states of dissolved organic matter (3DOM), which contribute to the degradation of environmental contaminants. An understanding of how DOM composition determines the production of reactive intermediates is useful for predictions of contaminant fate and for relating the environmental processing of DOM to its photochemistry. To compare the reactivity of common 3DOM probe compounds, the photoreactivity of diverse, environmentally relevant waters was quantified with trans,trans-hexadienoic acid, 2,4,6-trimethylphenol, and furfuryl alcohol under ambient and standardized conditions. Measurements with each probe, including apparent quantum yields and pseudo-steady state concentrations, were found to exhibit unique sensitivities to variation in solution conditions. Comparisons of apparent quantum yields under standardized conditions suggest that the probe compounds each react with different 3DOM populations. 3DOM photoreactivity varies with molecular weight, but the underlying mechanisms are unclear. Therefore, the photochemistry and composition of ultrafiltration-fractionated fulvic acid isolates were compared with reactive intermediate probes compounds and Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). Terrestrially derived DOM was increasingly aromatic with molecular weight, while microbially derived DOM was invariant. 3DOM pseudo-steady state concentrations decreased with molecular weight due to increased 3DOM quenching, rather than variation in 3DOM formation rates. In order to relate DOM processing in natural systems to altered composition and photoreactivity, DOM from related lakes of different trophic status was evaluated with FT-ICR MS and reactive intermediate probe compounds. The presence of highly aromatic formulas, similar to lignin and tannin, correlated with 3DOM formation and light absorbance. Conversely, aliphatic formulas correlated with enhanced 3DOM quantum yields and environmental persistence. To investigate the unique composition and photochemistry of DOM from aquatic microbial sources, DOM from a wastewater treatment plant was evaluated by FT-ICR MS and UV-visible spectroscopy. Wastewater DOM contained molecular formulas that were compositionally similar to lipids, proteins, carbohydrates, and lignin, and were enriched in heteroatoms such as N, S, P, and Cl. Secondary treatment increased highly aromatic formulas and increased the number of identified heteroatom containing formulas, while other treatment stages produced smaller changes in DOM composition.

Download or read book Towards an Understanding of Dissolved Organic Matter Molecular Composition and Reactivity in the Environment written by Barbara Cottrell and published by . This book was released on 2013 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Linking Optical and Chemical Properties of Dissolved Organic Matter in Natural Waters written by Christopher L. Osburn and published by Frontiers Media SA. This book was released on 2017-01-17 with total page 244 pages. Available in PDF, EPUB and Kindle. Book excerpt: A substantial increase in the number of studies using the optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) as a proxy for its chemical properties in estuaries and the coastal and open ocean has occurred during the last decade. We are making progress on finding the actual chemical compounds or phenomena responsible for DOM’s optical properties. Ultrahigh resolution mass spectrometry, in particular, has made important progress in making the key connections between optics and chemistry. But serious questions remain and the last major special issue on DOM optics and chemistry occurred nearly 10 years ago. Controversies remain from the non-specific optical properties of DOM that are not linked to discrete sources, and sometimes provide conflicting information. The use of optics, which is relatively easier to employ in synoptic and high resolution sampling to determine chemistry, is a critical connection to make and can lead to major advances in our understanding of organic matter cycling in all aquatic ecosystems. The contentions and controversies raised by our poor understanding of the linkages between optics and chemistry of DOM are bottlenecks that need to be addressed and overcome.

Download or read book Photochemistry of Dissolved Organic Matter written by Stephen Andrew Timko and published by . This book was released on 2014 with total page 145 pages. Available in PDF, EPUB and Kindle. Book excerpt: Constructed wetlands have the potential to provide low-energy treatment of pharmaceuticals and other micropollutants via photolysis. Natural dissolved organic matter (DOM) reacts with sunlight to produce reactive species such as singlet oxygen and excited triplet states of DOM that react quickly and efficiently with contaminants. To study the photo-chemistry of DOM, a unique solar-simulation system was developed, allowing for semi-continuous monitoring of absorbance and fluorescence spectra throughout the irradiation. This system was utilized to investigate the effect of solution pH on the fluorescence properties and degradation of DOM. For the first time, parallel factor (PARAFAC) analysis was utilized to deconvolute photo-labile, photo-stable, and pH- dependent fluorescent components during irradiation. Fluorescence is highly pH dependent, and as pH increases, the total amount of fluorescence loss, and the rate at which it is lost, increases significantly. This has important implications in treatment systems, as the photo-reactivity of DOM will change when pH gradients or fluctuations are observed. The photo-degradation of organic matter collected from a depth profile (0-4,500 m) the Sargasso Sea showed increased reactivity with increasing depth. Ultra-high resolution mass spectrometry (FT-MS) was used to characterize the samples, and correlation analyses between the fluorescence data and mass spectra revealed that high molecular weight, aromatic, and possibly polyphenolic compounds are contributing the most to the fluorescence properties that show the most reactivity in marine samples.Production of singlet oxygen, hydroxyl radical, and triplet excited states of DOM along two riverine transects in the Everglades were measured. The abundance of fluorescence PARAFAC components was compared to the reactive species production, and suggested that terrestrial organic matter may be more efficient producers of reactive species than microbial- or seagrass- derived organic matter.Finally, the relationship between optical properties of DOM samples collected around the world and their reactivity were investigated. Photo-irradiations and pH titrations were performed on all samples, and mass spectra collected via FT-MS. Humification indices, the biological index (BIX), and spectral slope from 275-295 nm were found to be most closely tied to changes in the mass spectra of the samples, and showed strong relationship to DOM source.

Download or read book Dissolved Organic Matter in Atmospheric Deposition written by Lidiia Iavorivska and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Dissolved organic matter (DOM) in the atmosphere affects air quality and climate. Unlike inorganic constituents that typically consist of single compounds, DOM is a mixture of multiple organic compounds having varying molecular weights, reactivity and solubility. Dissolved organic carbon (DOC) is typically used as a measure of the total DOM present in solution. In the atmosphere, DOC originates from emissions of various biogenic and anthropogenic sources, such as vegetation, incomplete combustion of fossil fuels, biomass burning, and sea-spray. The ultimate fate of atmospheric DOC is to be oxidized to inorganic forms of carbon dioxide and carbon monoxide, or to be removed from the atmosphere and transferred to the landscape through deposition. Deposition can occur as wet deposition via precipitation and as dry deposition via surface settling of particles and gases. The concentration, or quantity, of DOC in precipitation plays an important role in the carbon cycle and in other elemental cycles; while the chemical composition, or quality, of DOC in precipitation largely determines its fate in the environment. Rain and snow deposited to the landscape are a source of nutrient enrichment to ecosystems and water bodies, and are especially important as an input of carbon in coastal regions. Since DOC in precipitation is highly chemically reactive and bioavailable it influences rates of productivity in aquatic ecosystems. Despite the significance of DOC to many ecosystem processes, knowledge about its contributions to landscapes in precipitation remains limited. With anthropogenic influences on the carbon cycle now widely recognized, the need for synthesis of existing datasets on atmospheric deposition of DOC and further determining its rates and drivers is great. My dissertation is focused on wet deposition of DOC and assesses the magnitude and patterns of variation of organic matter in precipitation over space and time. The dissertation is organized into four manuscripts. Chapter 1 is a literature review where I provide a new data synthesis from 83 contemporary, peer-reviewed studies where organic carbon (OC) in precipitation was measured at sites around the world. Data regarding the concentrations of OC in precipitation and rates of atmospheric deposition were compiled in a common set of units and presented along with the summary statistics. These data give insights into the magnitude and regional variability of OC in precipitation. Organic carbon was ubiquitous in precipitation in rural and urban locations; with DOC in precipitation spanning several orders of magnitude between locations. This synthesis brings attention to atmospheric deposition as an under-sampled piece of the global carbon cycle; highlights gaps in data availability and challenges for data inter-comparison; and provides a unique data set that can be used for toward exploring future changes in the carbon cycle. Chapter 2 aims to understand how DOC concentration and composition in precipitation change temporally from storm to storm. Precipitation samples were collected at the Susquehanna Shale Hills Critical Zone Observatory watershed (Pennsylvania, USA) during 90 storm events. Observational data revealed temporal variability associated with seasonality and meteorological conditions. Using a mixed modeling statistical approach, I showed that there are multiple processes that work in synergy to influence the quantity and quality of DOC in precipitation. Factors related to storm properties, emission sources, and to the chemical composition of the atmosphere could explain more than 60% of the storm to storm variability in DOC concentrations. This study provided observations on changes in DOC that can be useful in modeling of atmospheric chemistry and in considering temporal changes in ecosystem nutrient balances and microbial activity.Chapter 3 explores how DOC concentration and composition vary throughout the course of storm events. I measured DOC in sequential samples during 13 storms at the Shale Hills watershed. The observational data generated hypotheses about potential factors that influence variability of DOC within storms. While previous studies have observed that concentrations of other elements in precipitation typically decrease over the course of individual storms, results from this study showed that DOC concentrations are highly variable. During most storms concentrations decreased towards the end of the event; however increasing concentrations in the later stages of some storms highlight that DOC removal with precipitation is not merely an exponential decay process. The variability of DOC during events is related to the balance between the cloud microphysics, atmospheric chemical transformations, and synoptic scale gradients in the abundance of organic compounds in the boundary layer. This work advances understanding of physicochemical processes occurring during storms that are relevant to studies of atmospheric chemistry, carbon cycling, and ecosystem responses.Chapter 4 quantifies spatial gradients in wet atmospheric DOC deposition across the state of Pennsylvania (USA). DOC concentrations were measured in selected precipitation samples collected for six years at a network of atmospheric deposition monitoring sites. A simple modeling approach was used to estimate the first statewide, annual estimates of wet atmospheric DOC deposition. Results showed that DOC inputs with wet deposition in Pennsylvania represented about one-third as much as literature reported values for DOC exported by rivers from watersheds in the region. The rates of DOC wet deposition showed a pronounced seasonality and spatial distribution, with highest deposition rates observed in the summer, especially at the sites located in western Pennsylvania.

Download or read book Advances in Understanding the Molecular Composition of Dissolved Organic Matter and Its Reactivity in the Environment written by Rajaa Mesfioui and published by . This book was released on 2014 with total page 304 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Temporal and Spatial Variability in the Quality of Dissolved Organic Matter in Ocean Systems written by Stuart Jerome Goldberg and published by ProQuest. This book was released on 2008 with total page 312 pages. Available in PDF, EPUB and Kindle. Book excerpt: Oceanic DOM is an important substrate that fuels heterotrophic bacterial activity, however, there is a paucity of data regarding the composition and quality of DOM in ocean systems. I analyzed the total carbohydrate (TCHO) and dissolved combined neutral sugar (DCNS) fractions of dissolved organic carbon (DOC), and mainly used TCHO and DCNS yields (% of DOC) to assess DOM quality over large temporal and spatial scales throughout the ocean.

Download or read book The Characterization of Dissolved Organic Matter and Its Influence on the Photochemical Fate of Antibiotics Used in Aquaculture written by Jennifer Julia Guerard and published by . This book was released on 2009 with total page 148 pages. Available in PDF, EPUB and Kindle. Book excerpt: The effects of source on dissolved organic matter composition were studied, and an intensive investigation was performed to characterize the photoreactivity of a fulvic acid isolated from Pony Lake on Cape Royds, Ross Island, Antarctica, a completely microbially-derived DOM end-member.

Download or read book Resolving Spatial and Temporal Variability in Dissolved Organic Matter Characteristics Within Combined Agricultural and Stormwater Conveyances written by Bryce A. Mihalevich and published by . This book was released on 2017 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: In many urban areas, stormwater runoff can threaten the ecological health of streams and downstream water bodies. Due to the increased impervious nature of urban landscapes, runoff is more 0́−flashy0́+ and as a result, high concentrations of pollutants can be transported in shorter periods of time than in more natural environments. One pollutant of concern is dissolved organic matter (DOM). DOM is important within aquatic ecosystems, but excess amounts can cause depletion in dissolved oxygen concentrations and can negatively affect aquatic organisms. This study investigated changes in DOM quantity and sources within the Northwest Field Canal (NWFC), an urban water conveyance located in Logan, Utah, USA that receives runoff during storm events. DOM was monitored at upstream and downstream locations within the canal and at selected stormwater outfalls within the study reach. During storm events, DOM concentrations were rapidly elevated to values orders of magnitude greater than in baseflow measurements, and were greater at the downstream site than at the upstream site, triggered by contributions from outfalls discharging into the canal. Changes in DOM composition during storm events confirmed that DOM is more terrestrially derived, whereas it is normally more microbially derived during baseflow conditions in the canal. These results provide better understanding of the composition of DOM in the canal system and may provide crucial information for future management of stormwater runoff that can potentially lead to the improvements of water quality in downstream water bodies.

Download or read book Direct and Indirect Photoreactions of Chromophoric Dissolved Organic Matter written by Jared Verrill Goldstone and published by . This book was released on 2002 with total page 278 pages. Available in PDF, EPUB and Kindle. Book excerpt: Photochemical transformations of chromophoric dissolved organic matter (CDOM) are one of the principal processes controlling its fate in coastal waters. The photochemical decomposition of CDOM leads to the formation of a variety of biologically available carbon substrates. Photomineralization of CDOM to dissolved inorganic carbon may constitute a significant flux in the global carbon cycle. Photoreactions ultimately lead to the destruction of the chromophores and hence to the loss of absorption and fluorescence (bleaching), thus acting as a sink for CDOM. Photodecomposition may proceed both via direct photochemical reactions, following absorption of photons by CDOM, or via indirect processes, involving DOM reactions with photochemically generated intermediates such as reactive oxygen species (ROS). The reactions of CDOM with two important ROS, superoxide (02- ) and hydroxyl radical (OH), have different consequences. Superoxide reactions with CDOM did not appear to degrade the CDOM. Instead, CDOM catalysed the dismutation of 02- to 02 and HOOH. This reactivity has the effect of limiting the steady-state concentration of 02- in most coastal waters. In contrast, reactions of CDOM with radiolytically produced OH formed CO2 and several low molecular weight carboxylic acids, as well as bleached both the absorption and fluorescence at slow rates. These reactions did not increase the bioavailability of this material to a microbial consortium. Both direct and indirect photochemical processes are expected to be accelerated by the presence of iron.

Download or read book Variability in the Photochemical Lability of Dissolved Organic Matter Within a Boreal Watershed written by Michael W. Hamilton and published by . This book was released on 2009 with total page 114 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Spectroscopic Characterization of Dissolved Organic Matter written by John Robert Helms and published by . This book was released on 2012 with total page 438 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Aquatic Organic Matter Fluorescence written by Paula G. Coble and published by Cambridge University Press. This book was released on 2014-07-14 with total page 407 pages. Available in PDF, EPUB and Kindle. Book excerpt: A core text on principles, laboratory/field methodologies, and data interpretation for fluorescence applications in aquatic science, for advanced students and researchers.