Study of Photochemical Formation of Hydroxyl Radical in Natural Waters

This dissertation mainly focuses on the sources of the hydroxyl radical (•OH) from photochemical reactions in natural waters, in particular from reactions involving dissolved organic matter (DOM). Firstly, an accurate method for estimating •OH formation rate during long-term irradiation was developed. It was observed that previous methods for measuring •OH formation rates in the natural waters, which were based upon sequentially determined cumulative concentrations of probe photoproducts, significantly underestimated actual •OH formation rates. It was found that the underestimation was mainly due to the degradation of the probe photoproducts and that only ‘instantaneous’ formation rates were appropriate for accurately estimating •OH photochemical formation rates. ‘Instantaneous’ •OH formation rates were obtained by adding probes to a sub-sample at each time point during the long-term irradiation and irradiating the sub-sample for a short time. By employing this approach, •OH formation rates were measured during a photoflocculation study in natural waters. In addition to •OH formation, hydrogen peroxide concentration, dissolved organic carbon, total dissolved nitrogen, water optical properties, and iron speciation were measured. The results showed that in iron- and DOM-rich water samples •OH appears to be mainly produced from the Fenton reaction initially, but subsequently from other sources, in particular DOM photoreactions. In order to elucidate possible photoreaction sites and mechanisms of •OH photoformation from DOM, phenolic compounds were used as model DOM chromophores. •OH quantum yields (Фs) at 280~340 nm were measured by •OH trapping reaction with benzene. It was found that many phenolic acids are capable of producing •OH, especially those with para hydroxyl and carboxyl groups (especially 2,4-dihydroxybenzoate and 4-hydrodroxybenzoate), which have markedly high •OH Фs. By conducting methane trapping and competition kinetics experiments, it was confirmed that free •OH was produced from these compounds. The results suggest that hydroxybenzoic acid moieties within DOM play an important role in the photoproduction of •OH. Finally, it was hypothesized that a quinoid enol tautomer present as a water cluster was responsible for •OH production from phenolic compounds with para hydroxyl and carboxyl groups. Phenolic acids with para hydroxyl and carbonyl groups are common components of lignin, which is a major source of DOM in freshwaters. In order to examine the lignin phenolic composition of natural samples, a simplified method using alkaline copper oxide oxidation coupled with solid-phase extraction and high performance liquid chromatography (HPLC) was developed. In this study, an interlaboratory comparison of the simplified HPLC approach with the conventional, but much more complex and expensive, high pressure reaction vessel GC-MS method was also conducted. The agreement between the two different methods was generally very good. A major benefit of this simplified HPLC method is that it allows any investigator with standard HPLC equipment to analyze lignin components, whereas previously only a small number of specialized labs were able to perform these analyses

Estimating Hydroxyl Radical Photochemical Formation Rates in Natural Waters During Long-Term Laboratory Irradiation Experiments

In this study it was observed that, during long-term irradiations (\u3e1 day) of natural waters, the methods for measuring hydroxyl radical (˙OH) formation rates based upon sequentially determined cumulative concentrations of photoproducts from probes significantly underestimate actual ˙OH formation rates. Performing a correction using the photodegradation rates of the probe products improves the ˙OH estimation for short term irradiations (\u3c1 day), but not long term irradiations. Only the ‘instantaneous’ formation rates, which were obtained by adding probes to aliquots at each time point and irradiating these sub-samples for a short time (≤2 h), were found appropriate for accurately estimating ˙OH photochemical formation rates during long-term laboratory irradiation experiments. Our results also showed that in iron- and dissolved organic matter (DOM)-rich water samples, ˙OH appears to be mainly produced from the Fenton reaction initially, but subsequently from other sources possibly from DOM photoreactions. Pathways of ˙OH formation in long-term irradiations in relation to H2O2 and iron concentrations are discussed

Comparison of a Simplified Cupric Oxide oxidation HPLC Method with the Traditional GC-MS Method for Characterization of Lignin Phenolics in Environmental Samples (vol 13, pg 1, 2015)

In our article entitled “Comparison of a simplified cupric oxide oxidation HPLC method with the traditional GC-MS method for characterization of lignin phenolics in environmental samples” (Limnol. Oceanogr.: Methods 13, 2015, 1–52), doi: 10.1002/lom3.10001, we would like to correct the errors in Fig. 2 and Table 2 as mentioned below. The label to Fig. 2(a) needs to be transposed as indicated in the corrected Fig. 2 image below

Molecular Nature of Marine Particulate Organic Iron-Carrying Moieties Revealed by Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS)

Marine sinking particulate organic matter (POM), acting as a link between surface primary production and burial of organic matter in marine sediments, undergoes a variety of physical and biochemical alterations on its way to the deep ocean, resulting in an increase in its un-characterizable proportion with diagenesis. Further, the binding ligands in POM for iron, an essential nutrient to marine life and tightly coupled with organic matter, has rarely been studied. In the current study, we employed an approach combining sequential extraction with ultrahigh resolution mass spectrometry (ESI-FTICRMS), in order to explore and unravel the chemical characteristics of organic matter compounds relevant to marine particle flux within the mesopelagic and deep ocean, with a focus on the potential iron-carrying molecules. With increasing depth, POM increases in aliphaticity, and decreases in intensity-normalized O/C ratios, aromatics, and carboxylic-rich alicyclic molecules (CRAM)-like compounds. The potential iron-carrying molecules account for ∼14% of total identified molecules, and appear to have been incorporated into the marine particles via ion complexation, hydrophobic interaction, and/or interlayered “occlusion.” The relative abundance of iron-binding organic molecules in these three operationally-defined categories changes with depth: “surficially-complexed” fraction decreases with depth, the “interlayered-occluded” fraction increases to a comparable extent and “hydrophobic interaction” fraction occurs at all depths. Collectively, the potential iron-carrying organic molecules exhibit a set of unique molecular characteristics: a relatively lower average H/C ratio and a higher O/C ratio compared to bulk POM, a dominance of aromatics, black carbon-like compounds and CRAM-like compounds, and minor amounts of aliphatics. These molecules exhibit partial similar molecular features as precursors formed from photochemical reactions in the surface ocean, but they have been greatly modified by flux processes. Noticeably, a minor fraction of these iron-carrying molecules

The Role of Microbial Exopolymers in Determining the Fate of Oil and Chemical Dispersants in the Ocean

The production of extracellular polymeric substances (EPS) by planktonic microbes can influence the fate of oil and chemical dispersants in the ocean through emulsification, degradation, dispersion, aggregation, and/or sedimentation. In turn, microbial community structure and function, including the production and character of EPS, is influenced by the concentration and chemical composition of oil and chemical dispersants. For example, the production of marine oil snow and its sedimentation and flocculent accumulation to the seafloor were observed on an expansive scale after the Deepwater Horizon oil spill in the Northern Gulf of Mexico in 2010, but little is known about the underlying control of these processes. Here, we review what we do know about microbially produced EPS, how oil and chemical dispersant can influence the production rate and chemical and physical properties of EPS, and ultimately the fate of oil in the water column. To improve our response to future oil spills, we need a better understanding of the biological and physiochemical controls of EPS production by microbes under a range of environmental conditions, and in this paper, we provide the key knowledge gaps that need to be filled to do so

Insights into the Photoproduction Sites of Hydroxyl Radicals by Dissolved Organic Matter in Natural Waters

The hydroxyl radical (^•OH) is the most reactive oxidant produced in natural waters. Photoproduction by chromophoric dissolved organic matter (CDOM) is one of its main sources, but the structures responsible for this production remain unknown. Here, a series of substituted phenol model compounds are examined to test whether these structures could act as a source of ^•OH. We find that many of these compounds do produce ^•OH with quantum yields (Φ) ranging from ∼10^–4 to ∼10^–2. In particular, two compounds that have hydroxy groups and carboxyl groups in a para relationship (4-hydroxybenzoic acid and 2,4-dihydroxybenzoic acid) exhibit relatively high Φ values, ∼10^–2. For 2,4-dihydroxybenzoic acid, the formation of ^•OH was confirmed through the use of competition kinetics and reaction with methane. We conclude that these types of structures, which may derive from polyphenolic source materials such as lignins, tannins, and humic substances, could be an important source of ^•OH in natural waters

Extracellular polymeric substances (EPS) producing and oil degrading bacteria isolated from the northern Gulf of Mexico.

Sinking marine oil snow was found to be a major mechanism in the transport of spilled oil from the surface to the deep sea following the Deepwater Horizon (DwH) oil spill. Marine snow formation is primarily facilitated by extracellular polymeric substances (EPS), which are mainly composed of proteins and carbohydrates secreted by microorganisms. While numerous bacteria have been identified to degrade oil, there is a paucity of knowledge on bacteria that produce EPS in response to oil and Corexit exposure in the northern Gulf of Mexico (nGoM). In this study, we isolated bacteria from surface water of the nGoM that grow on oil or Corexit dispersant. Among the 100 strains isolated, nine were identified to produce remarkable amounts of EPS. 16S rRNA gene analysis revealed that six isolates (strains C1, C5, W10, W11, W14, W20) belong to the genus Alteromonas; the others were related to Thalassospira (C8), Aestuariibacter (C12), and Escherichia (W13a). The isolates preferably degraded alkanes (17-77%), over polycyclic aromatic hydrocarbons (0.90-23%). The EPS production was determined in the presence of a water accommodated fraction (WAF) of oil, a chemical enhanced WAF (CEWAF), Corexit, and control. The highest production of visible aggregates was found in Corexit followed by CEWAF, WAF, and control; indicating that Corexit generally enhanced EPS production. The addition of WAF and Corexit did not affect the carbohydrate content, but significantly increased the protein content of the EPS. On the average, WAF and CEWAF treatments had nine to ten times more proteins, and Corexit had five times higher than the control. Our results reveal that Alteromonas and Thalassospira, among the commonly reported bacteria following the DwH spill, produce protein rich EPS that could have crucial roles in oil degradation and marine snow formation. This study highlights the link between EPS production and bacterial oil-degrading capacity that should not be overlooked during spilled oil clearance

Comparison of microgels, extracellular polymeric substances (EPS) and transparent exopolymeric particles (TEP) determined in seawater with and without oil

Extracellular polymeric substances (EPS), produced by microorganisms, are implicated for greatly influencing the fate of environmental contaminants, including oil. Transparent exopolymeric particles (TEP) are gel-like acidic polysaccharide particles that can be stained with Alcian blue, whereas Coomassie stainable particles (CSP) contain proteins and are stained with Coomassie brilliant blue. Marine microgels are reversibly formed from EPS. These terms are often used interchangeably, but they have rarely been measured simultaneously. Mesocosm and bottle experiments provided an opportunity to compare EPS, TEP, CSP and microgels in a water-accommodated fraction (WAF) of oil and seawater (control). Our results reveal that the biopolymers making up EPS, TEP and CSP consisted primarily of polysaccharides and proteins, mostly likely as proteoglycans and glycoproteins. Significant correlations were found between concentrations of TEP-C vs particulate organic carbon (POC), TEP-C vs particulate organic nitrogen (PON), TEP vs EPS, TEP vs CSP, TEP vs carbohydrates, proteins, CSP and carbohydrates, CSP vs proteins, and carbohydrates vs proteins. Chemical analysis of whole particles and colloids yielded both protein and polysaccharides concentrations higher than those in EDTA extraction, thus providing an upper limit of actual EPS contents in the particulate phase. The EPS that was electrostatically held onto particle surfaces (extractable by 1% EDTA) accounted for a minor (~4%) yet relatively constant proportion of TEP. Overall, the concentrations of the three terms ranked in the order of [gels] > [TEP] > [particulate EPS] in the water. Lastly, spectrophotometric methods have limitations in identifying complex or refractory polysaccharides, as evidenced by the comparison between NMR-quantified EPS and the total EPS determined by spectrophotometric methods. This study is the first time these terms were compared in the same sample. They provide useful information when reviewing historical TEP, CSP, EPS data collected field- and laboratory-studies, and provide linkages between them. In addition, they also demonstrate that they could provide complementary information relevant to ecosystem and flux studies