Tracking the evolution of particulate organic matter sources during summer storm events via end-member mixing analysis based on spectroscopic proxies.

Despite the growing attention to the effects of hydrological precipitation on organic carbon export along the continuum land-river-ocean, limited effort has been made to understand the export and the reactivity of particulate organic carbon (POC) compared to those of dissolved organic carbon (DOC). Yet, further understanding of the controlling mechanisms on the export of particulate organic matter (POM) from terrestrial systems is fundamental. In this study, we assessed the temporal changes of the source contributions to riverine POM in two adjacent rivers of the same watershed during two summer storm events, which included the early and the late events, using end-member mixing analysis (EMMA) based on spectroscopic proxies. The EMMA showed relatively high contributions of terrestrial materials to the riverine POM for both rivers during the early summer storm event. However, this trend did not persist until the late summer storm event, which presented the decreased contributions of the terrestrial sources and less dynamic changes in the source distributions compared to those observed in the early summer rain event. These results demonstrate the combined impacts of the land use/surrounding area, the hydrology, and the intra-seasonal variations on the dominant riverine POM sources. This study provides an interesting insight into the importance of the intense hydrological events on the export of the terrestrial OM and further on the potential modification of the existing carbon mass balance along the continuum land-river-ocean.

Do early diagenetic processes affect the applicability of commonly-used organic matter source tracking tools? An assessment through controlled degradation end-member mixing experiments.

In the development of organic matter (OM) source tracking tools, it is critical to validate if (1) the tracers are conservative with source mixing, and (2) they can be conservative under diagenetic processes (e.g., microbial degradation). In this study, these two critical points were rigorously tested for three commonly-used source tracking tools (i.e., absorbance and fluorescence proxies, stable carbon isotopes and lipid biomarkers) via a controlled experiment at laboratory scale. To this end, two end-members (e.g., soil and algae), which represent the most common and contrasted sources of OM to sediments in an aquatic environment, were mixed in different ratios and then incubated under different oxygen conditions (oxic versus anoxic) in the dark at 25 °C for 60 days. The initial and final signals of the source tracking tools were analyzed and compared for each mixing ratio. Based on three evaluation criteria concerning the linearity of the relationships, discrimination sensitivity, and conservative mixing behavior, we evaluated the applicability of the tools to trace the sediment organic matter in the aquatic environment. Although most of the source tracking proxies evaluated in this study showed a conservative nature after incubation, there are only a few that demonstrated both conservative behaviors with the sources mixing and under early diagenetic processes. The fluorescence proxies such as the relative distribution of a humic-like component associated with refractory source material (Ex/Em: 220/430 nm), modified fluorescence index (YFI), humification index (HIX), and carbon stable isotope ratios were identified to be the most reliable tracers for tracking sedimentary OM sources under early diagenetic processes. This study provides strong insights into the validation of common OM source tracking tools for sediment and a reasonable guideline to select the optimum indices for source discrimination via end-member mixing analysis.

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

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.

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

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.

Characterization of aquatic organic matter: Assessment, perspectives and research priorities.

Organic matter (OM) refers to the largest reactive reservoir of carbon-based compounds on Earth. Aside of its role as a source of carbon, OM is also actively involved in a wide range of ecological functions. It also plays an important role in the solubility, toxicity, bioavailability, mobility and distribution of pollutants. Therefore, OM is a key component in the local and global carbon cycle. About 12,000 articles containing organic matter in the title were published during the past decade, with a continuous increasing number each year (ISI Web of Science). Although this topic was widely explored and its interest has significantly increased, some limitations remain. These limitations can be technical (e.g., pre-treatment processes, low-resolution instrument, data handling) and can be related to the current approach. In this review, we first present the current strategies and tools to characterize the organic matter in the aquatic environment, then we tackle several aspects of current characterization limitations. Finally, we suggest new perspectives and priorities of research to improve the current limitations. From our point of view, simultaneous studies of particulate and dissolved OM fractions should be prioritized and multi-disciplinary approach, creation of databases, controlled experiments and collaborative works should be the next targets for future OM research priorities.

In-Depth Assessment of the Effect of Sodium Azide on the Optical Properties of Dissolved Organic Matter.

Treatment and preservation of samples are critical issues in measuring the optical properties of dissolved organic matter (DOM) due to their high sensitivity to physical and chemical changes upon sample handling. In this study, we rigorously assessed the potential interferences of sodium azide (NaN3) on DOM absorption and fluorescence. A wide range of different samples were poisoned with varying NaN3 concentrations. Several commonly used optical parameters derived from absorbance and fluorescence spectroscopy were compared at different samples and conditions to assess the interfering effect of NaN3. Our results showed that NaN3 altered the original features of absorbance and fluorescence even at the lowest level of the addition. The absorption coefficients of NaN3-treated samples increased up to 2608% at 254 nm and 66% at 280 nm relative to the untreated control. Fluorescence data revealed both a quenching effect and an enhancement in fluorescence. The effect of NaN3 on fluorescence was highly variable and affected by the NaN3 concentrations added, and the sources and the concentrations of DOM samples. None of these factors exhibited a clear linear behavior with NaN3 levels, making it difficult to develop a correction method. It can be recommended from the findings not to use NaN3 in preserving DOM samples for optical measurements.

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

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.

Faecal biomarkers can distinguish specific mammalian species in modern and past environments.

Identifying the presence of animals based on faecal deposits in modern and ancient environments is of primary importance to archaeologists, ecologists, forensic scientists, and watershed managers, but it has proven difficult to distinguish faecal material to the species level. Until now, four 5ß-stanols have been deployed as faecal biomarkers to distinguish between omnivores and herbivores, but they cannot distinguish between species. Here we present a database of faecal signatures from ten omnivore and herbivore species based on eleven 5ß-stanol compounds, which enables us to distinguish for the first time the faecal signatures of a wide range of animals. We validated this fingerprinting method by testing it on modern and ancient soil samples containing known faecal inputs and successfully distinguished the signatures of different omnivores and herbivores.

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.

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.

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.

The two popular source tracing tools of stable isotope ratios (δ13C and δ15N) 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).

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

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-ICR-MS), 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.

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

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 (AImod), 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.

Lipid biomarkers and spectroscopic indices for identifying organic matter sources in aquatic environments: A review.

Understanding the dynamics of organic matter (OM) and the roles in global and local carbon cycles is challenging to the fields of environmental sciences and biogeochemistry. The accurate identification of OM is an essential element to achieve this goal. Lipids, due to their ubiquitous presence and diagenetic and chemical stability, have long and successfully been used as molecular makers in assessing the sources and the fate of OM in natural environments. In parallel, optical properties of dissolved organic matter (DOM) have been suggested as efficient tools in tracing OM sources. In this review, three representative lipid biomarkers and several common spectroscopic indices were compared for their capabilities to identify OM sources in various aquatic environments. Spectroscopic indices present various benefits in term of the high sensitivity, easy and rapid analysis, and a low cost, providing reliable information on major sources (i.e., autochthonous, allochthonous and anthropogenic) of DOM in given systems investigated. However, for further understanding the associated biogeochemistry (e.g., diagenetic changes in sources), using biomarkers is preferable due to their abilities to identify a wide spectrum of different sources simultaneously as well as their high resolution for mixed OM sources. Thus, a complementary use of both tools is highly recommended for accurately tracking OM sources and the dynamics in aquatic systems, particularly in a watershed affected by multiple sources. Nevertheless, future studies need to be carried out (1) to refine the accuracy of the source assignments in a wide range of settings along with the development of an extensive database encompassing various sources, environmental factors, and geographical locations and (2) to understand how biogeochemical processes reflect the biomarkers and the spectroscopic indices used.

Sources and distribution of organic matter along the Ring of Cenotes, Yucatan, Mexico: sterol markers and statistical approaches.

The Yucatan Peninsula is a large low lying platform of limestone, dolomite and evaporite deposits, forming an extensive and mature karst aquifer with many sinkholes locally called cenotes. In Yucatan, the only source of drinking water is groundwater and its quality could be impaired by: (i) infiltration of contaminants and (ii) saltwater intrusion. To investigate the sources of organic matter in this aquifer, sediment samples (46) were collected from cenotes and analysed using gas chromatography-mass spectrometry. Sterol analysis, coupled with principal component analysis (PCA), allowed us to distinguish three sources of natural organic matter (e.g. marine, autotrophic and terrigenous) and to detect an anthropogenic input (e.g. fecal contamination). Good consistency was observed between the source assignment and the land use context (forest, agricultural, rural or urban areas) and the season, except for some of the samples where a direct correlation could not be made. The latter cases are most likely a result of the karstic character of the system.

Mixing and reaction kinetics in porous media: an experimental pore scale quantification.

We propose a new experimental set up to characterize mixing and reactive transport in porous media with a high spatial resolution at the pore scale. The analogous porous medium consists of a Hele-Shaw cell containing a single layer of cylindrical solid grains built by soft lithography. On the one hand, the measurement of the local, intrapore, conservative concentration field is done using a fluorescent tracer. On the other hand, considering a fast bimolecular reaction A + B → C occurring as A displaces B, we quantify the rate of product formation from the spatially resolved measurement of the pore scale reaction rate, using a chemiluminescent reaction. The setup provides a dynamical measurement of the local concentration field over 3 orders of magnitude and allows investigating a wide range of Péclet and Damköhler numbers by varying the flow rate within the cell and the local reaction rate. We use it to study the kinetics of the reaction front between A and B. While the advection-dispersion (Fickian) theory, applied at the continuum scale, predicts a scaling of the cumulative mass of product C as MC ∝ √t, the experiments exhibit two distinct regimes in which the produced mass MC evolves faster than the Fickian behavior. In both regimes the front rate of product formation is controlled by the geometry of the mixing interface between the reactants. Initially, the invading solute is organized in stretched lamellae and the reaction is limited by mass transfer across the lamella boundaries. At longer times the front evolves into a second regime where lamellae coalesce and form a mixing zone whose temporal evolution controls the rate of product formation. In this second regime, the produced mass of C is directly proportional to the volume of the mixing zone defined from conservative species. This interesting property is indeed verified from a comparison of the reactive and conservative data. Hence, for both regimes, the direct measurement of the spatial distribution of the pore scale reaction rate and conservative component concentration is shown to be crucial to understanding the departure from the Fickian scaling as well as quantifying the basic mechanisms that govern the mixing and reaction dynamics at the pore scale.

Extreme variability of steroid profiles in cow feces and pig slurries at the regional scale: implications for the use of steroids to specify fecal pollution sources in waters.

Thirty-five samples of cow feces (cowpat and cow manure) and pig slurries subjected to different treatment processes and different storage times before land spreading were extracted and analyzed by gas chromatography-mass spectrometry to determine their fecal stanol profiles. The fresh pig slurry data presented here increase considerably the classical range of values obtained for steroid ratios, resulting in an overlap with the range for cow feces. These results lead to the inability to distinguish species source of feces on the basis of steroid ratios alone. The cause of these differences is not known, although it appears likely to be related to differences in the metabolism of animals in relation to their age and/or variations in diet, rather than to secondary mechanisms of steroid degradation during storage or/and treatment of the feces. Nevertheless, the specificity of steroids to serve as a tool to differentiate cow feces from pig slurries is restored by considering the fecal stanol profile, notably, the six most diagnostic stanol compounds, which are 5ß-cholestan-3ß-ol (coprostanol), 5ß-cholestan-3α-ol (epicoprostanol), 24-methyl-5α-cholestan-3ß-ol (campestanol), 24-ethyl-5α-cholestan-3ß-ol (sitostanol), 24-ethyl-5ß-cholestan-3ß-ol (24-ethylcoprostanol), and 24-ethyl-5ß-cholestan-3α-ol (24-ethylepicoprostanol). In this study, chemometric analysis of the fingerprint of these six stanols using principal components analysis (PCA) distinguished pig slurries from cow feces. The application of PCA to the stanol profiles, as developed in this study, could be a promising tool for identifying the animal source in fecal contamination of waters.

Microbial and chemical markers: runoff transfer in animal manure-amended soils.

Fecal contamination of water resources is evaluated by the enumeration of the fecal coliforms and Enterococci. However, the enumeration of these indicators does not allow us to differentiate between the sources of fecal contamination. Therefore, it is important to use alternative indicators of fecal contamination to identify livestock contamination in surface waters. The concentration of fecal indicators (, enteroccoci, and F-specific bacteriophages), microbiological markers (Rum-2-bac, Pig-2-bac, and ), and chemical fingerprints (sterols and stanols and other chemical compounds analyzed by 3D-fluorescence excitation-matrix spectroscopy) were determined in runoff waters generated by an artificial rainfall simulator. Three replicate plot experiments were conducted with swine slurry and cattle manure at agronomic nitrogen application rates. Low amounts of bacterial indicators (1.9-4.7%) are released in runoff water from swine-slurry-amended soils, whereas greater amounts (1.1-28.3%) of these indicators are released in runoff water from cattle-manure-amended soils. Microbial and chemical markers from animal manure were transferred to runoff water, allowing discrimination between swine and cattle fecal contamination in the environment via runoff after manure spreading. Host-specific bacterial and chemical markers were quantified for the first time in runoff waters samples after the experimental spreading of swine slurry or cattle manure.