PARAFAC Modeling of Irradiation- and Oxidation-Induced Changes in Fluorescent Dissolved Organic Matter Extracted from Poultry Litter

Parallel factor analysis (PARAFAC) applied to fluorescence excitation emission matrices (EEMs) allows quantitative assessment of the composition of fluorescent dissolved organic matter (DOM). In this study, we fit a four-component EEM-PARAFAC model to characterize DOM extracted from poultry litter. The data set included fluorescence EEMs from 291 untreated, irradiated (253.7 nm, 310–410 nm), and oxidized (UV–H₂O₂, ozone) poultry litter extracts. The four components were identified as microbial humic-, terrestrial humic-, tyrosine-, and tryptophan-like fluorescent signatures. The Tucker’s congruence coefficients for components from the global (i.e., aggregated sample set) model and local (i.e., single poultry litter source) models were greater than 0.99, suggesting that the global EEM-PARAFAC model may be suitable to study poultry litter DOM from individual sources. In general, the transformation trends of the four fluorescence components were comparable for all poultry litter sources tested. For irradiation at 253.7 nm, ozonation, and UV–H₂O₂ advanced oxidation, transformation of the humic-like components was slower than that of the tryptophan-like component. The opposite trend was observed for irradiation at 310–410 nm, due to differences in UV absorbance properties of components. Compared to the other EEM-PARAFAC components, the tyrosine-like component was fairly recalcitrant in irradiation and oxidation processes. This novel application of EEM-PARAFAC modeling provides insight into the composition and fate of agricultural DOM in natural and engineered systems

Characterization of Dissolved Organic Matter in Full Scale Continuous Stirred Tank Biogas Reactors Using Ultrahigh Resolution Mass Spectrometry: A Qualitative Overview

Dissolved organic matter (DOM) was characterized in eight full scale continuous stirred tank biogas reactors (CSTBR) using solid-phase extraction and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). An overview of the DOM molecular complexity in the samples from biogas reactors with conventional operational conditions and various substrate profiles is provided by assignments of unambiguous exact molecular formulas for each measured mass peak. Analysis of triplicate samples for each reactor demonstrated the reproducibility of the solid-phase extraction procedure and ESI-FT-ICR-MS which allowed precise evaluation of the DOM molecular differences among the different reactors. Cluster analysis on mass spectrometric data set showed that the biogas reactors treating sewage sludge had distinctly different DOM characteristics compared to the codigesters treating a combination of organic wastes. Furthermore, the samples from thermophilic and mesophilic codigesters had different DOM composition in terms of identified masses and corresponding intensities. Despite the differences, the results demonstrated that compositionally linked organic compounds comprising 28–59% of the total number of assigned formulas for the samples were shared in all the reactors. This suggested that the shared assigned formulas in studied CSTBRs might be related to common biochemical transformation in anaerobic digestion process and therefore, performance of the CSTBRs

Table_1_A pilot study suggests the correspondence between SAR202 bacteria and dissolved organic matter in the late stage of a year-long microcosm incubation.XLSX

SAR202 bacteria are abundant in the marine environment and they have been suggested to contribute to the utilization of recalcitrant organic matter (RDOM) within the ocean’s biogeochemical cycle. However, this functional role has only been postulated by metagenomic studies. During a one-year microcosm incubation of an open ocean microbial community with lysed Synechococcus and its released DOM, SAR202 became relatively more abundant in the later stage (after day 30) of the incubation. Network analysis illustrated a high degree of negative associations between SAR202 and a unique group of molecular formulae (MFs) in phase 2 (day 30 to 364) of the incubation, which is empirical evidence that SAR202 bacteria are major consumers of the more oxygenated, unsaturated, and higher-molecular-weight MFs. Further investigation of the SAR202-associated MFs suggested that they were potentially secondary products arising from initial heterotrophic activities following the amendment of labile Synechococcus-derived DOM. This pilot study provided a preliminary observation on the correspondence between SAR202 bacteria and more resistant DOM, further supporting the hypothesis that SAR202 bacteria play important roles in the degradation of RDOM and thus the ocean’s biogeochemical cycle.</p

Selective Chlorination of Natural Organic Matter: Identification of Previously Unknown Disinfection Byproducts

Natural organic matter (NOM) serve as precursors for disinfection byproducts (DBPs) in drinking water production making NOM removal essential in predisinfection treatment processes. We identified molecular formulas of chlorinated DBPs after chlorination and chloramination in four Swedish surface water treatment plants (WTPs) using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chlorine-containing formulas were detected before and after disinfection and were therefore classified to identify DBPs. In total, 499 DBPs were detected, of which 230 have not been reported earlier. The byproducts had, as a group, significantly lower ratio of hydrogen to carbon (H/C) and significantly higher average carbon oxidation state (C_OS), double bond equivalents per carbon (DBE/C) and ratio of oxygen to carbon (O/C) compared to Cl-containing components present before disinfection and CHO formulas in samples taken both before and after disinfection. Electrophilic substitution, the proposed most significant reaction pathway for chlorination of NOM, results in carbon oxidation and decreased H/C while O/C and DBE/C is left unchanged. Because the identified DBPs had significantly higher DBE/C and O/C than the CHO formulas we concluded that chlorination of NOM during disinfection is selective toward components with relatively high double bond equivalency and number of oxygen atoms per carbon. Furthermore, choice of disinfectant, dose, and predisinfection treatment at the different WTPs resulted in distinct patterns in the occurrence of DBP formulas

Data_Sheet_1_A pilot study suggests the correspondence between SAR202 bacteria and dissolved organic matter in the late stage of a year-long microcosm incubation.DOCX

SAR202 bacteria are abundant in the marine environment and they have been suggested to contribute to the utilization of recalcitrant organic matter (RDOM) within the ocean’s biogeochemical cycle. However, this functional role has only been postulated by metagenomic studies. During a one-year microcosm incubation of an open ocean microbial community with lysed Synechococcus and its released DOM, SAR202 became relatively more abundant in the later stage (after day 30) of the incubation. Network analysis illustrated a high degree of negative associations between SAR202 and a unique group of molecular formulae (MFs) in phase 2 (day 30 to 364) of the incubation, which is empirical evidence that SAR202 bacteria are major consumers of the more oxygenated, unsaturated, and higher-molecular-weight MFs. Further investigation of the SAR202-associated MFs suggested that they were potentially secondary products arising from initial heterotrophic activities following the amendment of labile Synechococcus-derived DOM. This pilot study provided a preliminary observation on the correspondence between SAR202 bacteria and more resistant DOM, further supporting the hypothesis that SAR202 bacteria play important roles in the degradation of RDOM and thus the ocean’s biogeochemical cycle.</p

Changes in Dissolved Organic Matter during the Treatment Processes of a Drinking Water Plant in Sweden and Formation of Previously Unknown Disinfection Byproducts

The changes in dissolved organic matter (DOM) throughout the treatment processes in a drinking water treatment plant in Sweden and the formation of disinfection byproducts (DBPs) were evaluated by using ultra-high-resolution mass spectrometry (resolution of ∼500000 at <i>m</i>/<i>z</i> 400) and nuclear magnetic resonance (NMR). Mass spectrometric results revealed that flocculation induced substantial changes in the DOM and caused quantitative removal of DOM constituents that usually are associated with DBP formation. While half of the chromophoric DOM (CDOM) was removed by flocculation, ∼4–5 mg L^–1 total organic carbon remained in the finished water. A conservative approach revealed the formation of ∼800 mass spectrometry ions with unambiguous molecular formula assignments that contained at least one halogen atom. These molecules likely represented new DBPs, which could not be prevented by the flocculation process. The most abundant <i>m</i>/<i>z</i> peaks, associated with formed DBPs, could be assigned to C₅HO₃Cl₃, C₅HO₃Cl₂Br, and C₅HO₃ClBr₂ using isotope simulation patterns. Other halogen-containing formulas suggested the presence of halogenated polyphenolic and aromatic acid-type structures, which was supported by possible structures that matched the lower molecular mass range (maximum of 10 carbon atoms) of these DBPs. ¹H NMR before and after disinfection revealed an ∼2% change in the overall ¹H NMR signals supporting a significant change in the DOM caused by disinfection. This study underlines the fact that a large and increasing number of people are exposed to a very diverse pool of organohalogens through water, by both drinking and uptake through the skin upon contact. Nontarget analytical approaches are indispensable for revealing the magnitude of this exposure and to test alternative ways to reduce it

Fluorescence Fingerprinting of Bottled White Wines Can Reveal Memories Related to Sulfur Dioxide Treatments of the Must

For the first time, Excitation Emission Matrix (EEM) fluorescence spectroscopy was combined with parallel factor statistical analysis (PARAFAC) and applied to a set of 320 dry white wines of the Chardonnay grape variety. A four component PARAFAC model (C1, C2, C3 and C4) best explained the variability of fluorescence signatures of white wines. Subtle changes were observed in EEMs of white wines from two different vintages (2006 and 2007), where different concentrations of sulfur dioxide (0, 4, and 8 g·hL^–1) were added to the grape must at pressing. PARAFAC results clearly indicated that sulfur dioxide added to the must subsequently influenced white wine chemistry into three distinct sulfur dioxide dose-dependent aging mechanisms. For both vintages, C1 and C2 were the dominant components affected by sulfur dioxide and likely reacting with phenolic compounds associated with some presumably proteinaceous material. Distinct component combinations revealed either SO₂ dependent or vintage-dependent signatures, thus, showing the extent of the complex versatile significance underlying such fluorescence spectra, even after several years of bottle aging