Comparing discrimination capabilities of fluorescence spectroscopy versus FT-ICR-MS for sources and hydrophobicity of sediment organic matter

Derrien, Morgane,Lee, Yun Kyung,Shin, Kyung-Hoon,Hur, Jin Springer-Verlag 2018 Environmental Science and Pollution Research Vol.25 No.2

<P>Characterizing the chemical and molecular composition of sediment organic matter (SeOM) provides critical information for a complete picture of global carbon and nutrient cycles, and helps to track the sources and the fate of organic carbon in aquatic environments. In this study, we examined fluorescence properties and the molecular composition of the alkaline-extractable organic matter (AEOM) of sediments in a coastal lake (Lake Sihwa) and its surrounding creeks (rural, urban, wetland, and industrial areas). Five fluorescence-based indices and 20 molecular parameters were selected from fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS), respectively, and utilized to discriminate the AEOM among five different sources as well as the chemical composition of hydrophobic acid (HoA) and hydrophilic (Hi) fractions. Ordination based on Bray-Curtis dissimilarity matrices showed that the fluorescence-based indices distinguished among urban, lake, and the three other sources, while the molecular parameters from FT-ICR-MS performed better in discriminating among the sources of rural, wetland, and industrial areas. Irrespective of the sources, the two different chemical fractions were statistically distinguished by their relative distributions of the UVA-humic-like fluorescent component and the carbohydrate molecular group. However, a rigorous test based on percent dissimilarities indicated no superior capability of either of the two tools in discriminating the sources or their two chemical fractions, which might be attributed to the inherent structural heterogeneity of SeOM and the limited analytical window of FT-ICR-MS for relatively large-sized molecules.</P>

Estimation of different source contributions to sediment organic matter in an agricultural-forested watershed using end member mixing analyses based on stable isotope ratios and fluorescence spectroscopy

Derrien, Morgane,Kim, Min-Seob,Ock, Giyoung,Hong, Seongjin,Cho, Jinwoo,Shin, Kyung-Hoon,Hur, Jin Elsevier 2018 Science of the Total Environment Vol.618 No.-

<P><B>Abstract</B></P> <P>The two popular source tracing tools of stable isotope ratios (δ<SUP>13</SUP>C and δ<SUP>15</SUP>N) and fluorescence spectroscopy were used to estimate the relative source contributions to sediment organic matter (SeOM) at five different river sites in an agricultural-forested watershed (Soyang Lake watershed), and their capabilities for the source assignment were compared. Bulk sediments were used for the stable isotopes, while alkaline extractable organic matter (AEOM) from sediments was used to obtain fluorescent indices for SeOM. Several source discrimination indices were fully compiled for a range of the SeOM sources distributed in the catchments of the watershed, which included soils, forest leaves, crop (C3 and C4) and riparian plants, periphyton, and organic fertilizers. The relative source contributions to the river sediment samples were estimated via end member mixing analysis (EMMA) based on several selected discrimination indices. The EMMA based on the isotopes demonstrated that all sediments were characterized by a medium to a high contribution of periphyton ranging from ~30% to 70% except for one site heavily affected by forest and agricultural fields with relatively high contributions of terrestrial materials. The EMMA based on fluorescence parameters, however, did not show similar results with low contributions from forest leaf and periphyton. The characteristics of the studied watershed were more consistent with the source contributions determined by the isotope ratios. The discrepancy in the EMMA capability for source assignments between the two analytical tools can be explained by the limited analytical window of fluorescence spectroscopy for non-fluorescent dissolved organic matter (FDOM) and the inability of AEOM to represent original bulk particulate organic matter (POM).</P> <P><B>Highlights</B></P> <P> <UL> <LI> Different sources samples were characterized using fluorescence and stable isotopes. </LI> <LI> Relative source contributions of SeOM were estimated by EMMA. </LI> <LI> The results of EMMAs were compared with isotope versus fluorescence parameters. </LI> <LI> Inability of AEOM of sediments to represent original bulk POM was highlighted. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Assessment on applicability of common source tracking tools for particulate organic matter in controlled end member mixing experiments

Derrien, Morgane,Shin, Kyung-Hoon,Hur, Jin Elsevier 2019 Science of the Total Environment Vol.666 No.-

<P><B>Abstract</B></P> <P>In this study, ideal mixing behaviors of the three commonly-used source tracking tools, which include fluorescence spectroscopy, stable isotope ratios, and lipid biomarkers, were evaluated in controlled particular organic matter (POM) mixtures of two contrasting end members e.g., soil and algae. In parallel, three different extraction methods based on water (WEOM) and two alkaline solutions were compared to identify the preferential pre-treatment option that leads to a good performance of the spectroscopic source tracking indices on the dissolved organic matter (DOM) extracted from the POM. Based on three evaluation criteria concerning the linearity of the relationships, the discrimination sensitivity, and the conservative mixing behavior of fourteen tested indices, the fluorescence proxies such as the relative distribution of the fluorescence components and the modified fluorescence index YFI of the WEOM were found to be reliable and robust indices for POM source tracking. The carbon stable isotope ratios of the POM samples exhibited an ideal mixing behavior even after the DOM extraction, while the biomarkers of sterols/stanols did not present a good linear and conservative behavior at similar conditions. In addition, the WEOM was identified as the preferred extraction method for the application of spectroscopic indices for POM source discrimination. This study provides a guideline to select the optimum indices for the POM source discrimination via the end member mixing analysis.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Conservative behaviors of three classical source tracking indices are examined for POM mixtures. </LI> <LI> Optical indices, δ<SUP>13</SUP>C, and lipid biomarkers are compared in parallel. </LI> <LI> Different mixing behaviors (linear or nonlinear) are identified for the tested tacking tools. </LI> <LI> δ<SUP>13</SUP>C, relative abundance of fluorescent components, and YFI are good tracking indices. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Biodegradation-induced signatures in sediment pore water dissolved organic matter: Implications from artificial sediments composed of two contrasting sources

Derrien, Morgane,Shin, Kyung-Hoon,Hur, Jin Elsevier 2019 Science of the Total Environment Vol.694 No.-

<P><B>Abstract</B></P> <P>Biodegradation is one of the main processes causing the changes in amount, composition and properties of organic matter in sediment and water-sediment interface. The degradation processes of sediment organic matter lead to a release of dissolved organic matter (DOM) into the pore water via hydrolysis and depolymerization of particulate organic matter (POM). Whereas the pore waters represent a reactive zone in sediment closely linked to biogeochemistry of the substrate, they are still poorly characterized under diagenetic processes. In this study, we examined the DOM alterations in sediment pore water originating from the mixtures of two contrasting POM sources at known ratios through controlled incubation experiments with two different oxygen conditions (i.e., oxic versus anoxic). The changes in pore water DOM were tracked using fluorescence and absorbance spectroscopy and size exclusion chromatography. The results based on the sediments artificially mixed of two end-member sources (e.g., soil and algae) showed that the most affected parameter during the biodegradation process was the amount of the pore water DOM. It was also demonstrated that the changes in the spectroscopic and molecular properties were more dependent on the POM sources and the mixing ratios rather than on the oxygen conditions. This study provides insights into the responding features of DOM in a reactive sediment zone as pore water to the main biogeochemical process.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Degradation-induced changes were examined for sediment pore water DOM. </LI> <LI> DOC is the most affected parameter of sediment pore water by biodegradation. </LI> <LI> Mixing ratios of POM sources in sediment highly affect the pore water DOM properties. </LI> <LI> Oxygen does not affect biodegradation-induced alterations as much as sediment sources. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Spectroscopic and molecular characterization of humic substances (HS) from soils and sediments in a watershed: comparative study of HS chemical fractions and the origins

Derrien, M.,Lee, Y. K.,Park, J. E.,Li, P.,Chen, M.,Lee, S. H.,Lee, S. H.,Lee, J. B.,Hur, J. Springer Science + Business Media 2017 Environmental Science and Pollution Research Vol.24 No.20

<P>Optical properties and molecular composition of humic substances (HS) can provide valuable information on the sources and the history of the associated biogeochemical processes. In this study, many well-known spectral and molecular characteristics were examined in eight different HS samples, which were extracted from soils and sediments located in a forested watershed, via two advanced tools including fluorescence excitation emission matrix-parallel factor analysis (EEM-PARAFAC) and high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Two humic-like (C1 and C2) and one protein-like (C3) components were identified from EEM-PARAFAC. Irrespective of the origins, humic acid (HA) fractions were distinguished from fulvic acid (FA) fractions by the HS characteristics of specific UV absorbance (SUVA), the number of formulas, maximum fluorescence intensities of C1 and C2, condensed aromatics, tannins, and CHON, CHOS, and CHONS classes. In contrast, only five HS indices, including C3 intensity, H%, modified aromatic index (AI(mod)), the percentages of carbohydrates, and unsaturated hydrocarbons, were found to be significant factors in discriminating between the two HS origins (i.e., soils and sediments). The ordination of the Bray-Curtis dissimilarity matrix further confirmed that the HS chemical fraction (i.e., HA or FA) was the more important factor to determine the measured HS characteristics than the HS origin. Our results provided an in-depth insight into the chemical and structural heterogeneity of bulk HS, which could be even beyond the differences observed along the two HS origins. This study also delivers a cautious message that the two operationally defined HS chemical fractions should be carefully considered in tracking the origins of different HS samples.</P>

Resonance Region Nuclear Data Analysis to Support Advanced Fuel Cycle Development

M. E. Dunn,H. Derrien,L. C. Leal,C. Gil,김도헌 한국물리학회 2011 THE JOURNAL OF THE KOREAN PHYSICAL SOCIETY Vol.59 No.23

The Oak Ridge National Laboratory (ORNL) and the Korean Atomic Energy Research Institute (KAERI) are performing collaborative research as part of a three-year United States (U.S.)-Republic of Korea (ROK) International Nuclear Energy Research Initiative (I-NERI) project to provide improved neutron cross-section data with uncertainty or covariance data important for advanced fuel cycle and nuclear safeguards applications. ORNL and KAERI have initiated efforts to prepare new cross-section evaluations for ^(240)Pu, ^(237)Np, and the stable Cm isotopes. At the current stage of the I-NERI project, ORNL has recently completed a preliminary resonance-region cross-section evaluation with covariance data for ^(240)Pu and has initiated resonance evaluation efforts for ^(237)Np and ^(244)Cm. Likewise, KAERI is performing corresponding high-energy cross-section analyses (i.e., above the resonance region) for the noted isotopes. The paper provides results pertaining to the new resonance region evaluation efforts with emphasis on the new ^(240)Pu evaluation.

Evaluation of the Chromium Resonance Parameters Including Resonance Parameter Covariance

L. Leal,H. Derrien,K. Guber,G. Arbanas,D. Wiarda 한국물리학회 2011 THE JOURNAL OF THE KOREAN PHYSICAL SOCIETY Vol.59 No.23

The intent of this work is to report the results and describe the procedures utilized to evaluate the chromium isotopes' cross sections, i.e., ^(50)Cr, ^(52)Cr, ^(53)Cr, and ^(54)Cr, for criticality safety applications. The evaluations were done in the resolved resonance region using the reduced Reich-Moore R-matrix formalism. The novel aspect of this evaluation is the inclusion of new transmission and capture cross-section measurements performed at the Oak Ridge Electron Linear Accelerator (ORELA) for energies below 100 keV and the extension of the ^(53)Cr energy region. The resonance analysis was performed with the multilevel R-matrix code, SAMMY, which utilizes the generalized least-squares technique based on the Bayes' theory. Complete sets of resonance parameters and resonance parameter covariance matrices (RPCMs) were obtained for each of the chromium isotopes from the SAMMY analysis of the experimental database.

Evaluating the contributions of different organic matter sources to urban river water during a storm event via optical indices and molecular composition

Lee, Mi-Hee,Lee, Yun Kyung,Derrien, Morgane,Choi, Kwangsoon,Shin, Kyung Hoon,Jang, Kyoung-Soon,Hur, Jin Elsevier 2019 Water research Vol.165 No.-

<P><B>Abstract</B></P> <P>Dissolved organic matter (DOM) in river water dynamically changes with respect to its major sources during heavy rain events. However, there has been no established tool to estimate the relative contributions of different organic sources to river water DOM. In this study, the evolution in the contributions of ten different organic matter (OM) sources to storm water DOM was explored with a selected urban river, the Geumho River in South Korea, during storm events via an end-member mixing analysis (EMMA) based on fluorescence indices and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The OM source materials included treated effluent, road runoff, groundwater, topsoil, deep soil, leaves, reeds, riparian plants, attached algae, and suspended algae. The EMMA results provided quantitative estimates of the variations in the dominant OM sources with the progress of storms. Treated effluent was the prevailing source at the beginning period of the storm, while topsoil, leaves, riparian plants, and groundwater predominated during and after the peak period. The fluorescence indices-based evaluation was consistent with the statistical comparison of the molecular formulas derived from FT-ICR-MS conducted on the ten potential OM sources and the storm samples. The observed variations in the OM sources agreed with the typical characteristics of urban rivers in connection with anthropogenic inputs and the impact of surrounding impervious surfaces. This study demonstrates the application of intuitive and facile tools in estimating the relative impacts of OM sources in urban watersheds.</P> <P><B>Highlights</B></P> <P> <UL> <LI> It is the first study using FT-ICR-MS for OM source tracking during a storm. </LI> <LI> A quantitative evaluation is firstly performed for dynamic variations in DOM sources. </LI> <LI> Treated effluent and top soil prevailed before and after peak, respectively. </LI> <LI> Optical indices-based EMMA results were consistent with FT-ICR-MS data. </LI> <LI> The EMMA provided a reliable tool for OM source tracking for urban watersheds. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Optical and molecular characterization of dissolved organic matter (DOM) in the Arctic ice core and the underlying seawater (Cambridge Bay, Canada): Implication for increased autochthonous DOM during ice melting

Retelletti Brogi, Simona,Ha, Sun-Yong,Kim, Kwanwoo,Derrien, Morgane,Lee, Yun Kyung,Hur, Jin Elsevier 2018 Science of the Total Environment Vol.627 No.-

<P><B>Abstract</B></P> <P>Sea ice contains a large amount of dissolved organic matter (DOM), which can be released into the ocean once it melts. In this study, Arctic sea ice DOM was characterized for its optical (fluorescence) properties as well as the molecular sizes and composition via size exclusion chromatography and Fourier transformation ion cyclotron resonance mass spectrometry (FT-ICR MS). Ice cores were collected along with the underlying seawater samples in Cambridge Bay, an Arctic area experiencing seasonal ice formation. The ice core samples revealed a marked enrichment of dissolved organic carbon (DOC) compared to the seawater counterparts (up to 6.2 times greater). The accumulation can be attributed to in situ production by the autotrophic and heterotrophic communities. Fluorescence excitation emission matrices (EEMs) elaborated with parallel factor analysis (PARAFAC) evidenced the prevalence of protein-like substances in the ice cores, which likely results from in situ production followed by accumulation in the ice. Size exclusion chromatography further revealed the in situ production of all DOM size fractions, with the exception of the humic substance fraction. The majority of DOM in both the ice and seawater consists of low molecular weight compounds (<350 Da) probably derived by the microbial degradation/transformation of freshly produced DOM. Molecular characterization also supported the in situ production of DOM and highlighted the marked difference in molecular composition between sea ice and seawater. This study provides new insights into the possible role of sea ice DOM in the Arctic carbon cycle under climate change.</P> <P><B>Highlights</B></P> <P> <UL> <LI> A comparative study for Arctic sea ice and the underlying seawater DOM </LI> <LI> Multiple DOM analyses including FT-ICR MS and SEC are utilized for the first time. </LI> <LI> A net accumulation of in situ-produced DOM was observed in the ice. </LI> <LI> Large amounts of labile small-sized DOM could be annually released upon ice melting. </LI> <LI> This work provides a new insight into DOM composition changes under ice melting. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>