Fluorescent Dissolved Organic Matter Research Articles

Characterization of Dissolved Organic Matter from Agricultural and Livestock Effluents: Implications for Water Quality Monitoring.

There is growing concern about the impact of agricultural practices on water quality. The loss of nutrients such as nitrogen and phosphorous through agricultural runoff poses a potential risk of water quality degradation. However, it is unclear how dissolved organic matter (DOM) composition is associated with pollution levels in water bodies. To address this, we conducted a cross-year investigation to reveal the nature of DOM and its relationship to water quality in agricultural effluents (AEs) and livestock effluents (LEs). We discovered that DOM fluorescence components of AEs were mainly from autochthonous and terrestrial sources, while in LEs it was primarily from autochthonous sources. LEs showed a higher β:α and biological index (BIX) than AEs, indicating that LEs had higher biological activity. Compared to the LEs, DOM in AEs exhibited a higher humification index (HIX), illustrating that DOM was more humic and aromatic. Overall, our results suggest that the BIX and fluorescence index (FI) were best suited for the characterization of water bodies impacted by LEs and AEs. Excitation-emission matrix spectroscopy and parallel factor (EEMs-PARAFAC) analysis showed that DOM in AEs was mainly a humic-like material (~64%) and in LEs was mainly protein-like (~68%). Tryptophan-like compounds (C1) were made more abundant in AEs because of the breakdown of aquatic vegetation. The microbial activity enhanced protein-like substances (C1 and C2) in LEs. Our study revealed a positive correlation between five-day biochemical oxygen demand (BOD5) concentrations and tyrosine-like substance components, suggesting that fluorescence peak B may be a good predictor of water quality affected by anthropogenic activities. For both LEs and AEs, our results suggest that peak D may be a reliable water quality surrogate for total phosphorus (TP).

The impact of inorganic ions on the solar photolysis of chlorinated dissolved organic matter from different sources: Spectral characteristics, disinfection byproducts, and biotoxicities

Dissolved organic matter (DOM) from wastewater treatment plant (WWTP) effluent is chlorinated and then discharged into natural waters, where it is subject to solar irradiation. However, the impacts of inorganic ions in natural waters on the photochemical transformations of the chlorinated DOM (DOM-Cl) have not been studied comprehensively. In this study, variations in the spectral characteristics, disinfection byproducts (DBPs), and biotoxicities of DOM-Cl under solar irradiation at different pH values and in the presence of NO3- and HCO3- were revealed. Three sources of DOM, including DOM from a WWTP effluent, natural organic matter from the Suwannee River, and DOM from plant leaf leachate, were investigated. Solar irradiation resulted in the oxidation of the highly reactive aromatic structures and then reduced the amounts of chromophoric and fluorescent DOM, especially under alkaline conditions. Moreover, alkaline conditions significantly promoted the detected DBPs degradation and the biotoxicities attenuation, while NO3- and HCO3- generally impeded them (or did not work). Dehalogenation of the unknown halogenated DBPs and photolysis of the nonhalogenated organics were the main mechanisms for the DOM-Cl biotoxicity reductions. Hence, improving the ecological safety of WWTP effluents could be achieved through solar irradiation by removing the DBPs formed.

Application of PARAFAC Technique to Compare Fluorescence Property of Different Dissolved Organic Matters

Objectives : It provides a detailed procedure for analyzing dissolved organic matter (DOM) by the PARAFAC technique and aims to identify compare different fluorescent components of DOM with various water sources.Methods : PARAFAC modeling was performed based on the PARAFAC tutorial by Stedmon et al. [11] using a total of 160 samples originated from wetlands, river, wastewater treatment plant influent and effluent. The procedure includes data preprocessing, initial model creation, outlier analysis, split-half analysis, core consistency, and sum of squared error analysis (SSE). After finishing the model validation step, the samples were analyzed through the verified PARAFAC model.Results and Discussion : An initial model with 2 to 4 components was created, and as a result of outlier analysis, the four WWTP Influent samples were removed as outliers. As a result of SSE analysis, the model with two components has a relatively higher SSE value than the model with three or four components. In the case of core consistency, the model with 2, 3, and 4 components scored 99.6%, 94.9%, and 65.7%, respectively. As a result of the split-half analysis, the spectra of the model having the three components of the split data were the same, so it was finally determined that the number of three components was appropriate in the model. The DOM samples were analyzed by the developed PARAFAC model. It was confirmed that the ratio of humic components was higher in the order of WWTP effluent ≈ wetland > river > WWTP influent, and the ratio of protein components affected by microbial activity was in the order of WWTP influent > river > wetland ≈ WWTP effluent.Conclusion : In this paper, the procedure of PARAFAC modeling was described and the DOM fluorescence properties were compared. This research provides a practical method for increasing the utilization of the PARAFAC model in the water treatment research field. In addition, the result of the PARAFAC model is useful data to control DOM efficiently in water treatment facilities.

Recalcitrant dissolved organic carbon release and production from aquatic plants leachate

Leached dissolved organic matter (DOM) from withered aquatic plants plays a critical role as a nutrient source for coastal waters, and potentially contributes to marine carbon fixation. In this study, withered seaweed (Ecklonia cava) and seagrass (Zostera japonica) were incubated under laboratory conditions to estimate the amount and decomposition properties of the resulting leached dissolved organic carbon (DOC) and fluorescence dissolved organic matter (FDOM). Concentrations of leached DOC from E. cava were higher than those from Z. japonica because the cell walls of the former were relatively more easily degraded and hydrolyzed than those of the latter. As humic-like fluorescence increased from the beginning of the incubation period, it was inferred that recalcitrant DOC (RDOC) leached directly from withered aquatic plants. Additionally, recalcitrant component production was attributed to the microbial carbon pump using labile DOC. Leached RDOC from withered aquatic plants contributes to blue carbon and CO2 uptake by photosynthesis.

Interactions between particulate organic matter and dissolved organic matter in a weak dynamic bay revealed by stable isotopes and optical properties

Few studies have incorporated the tools of stable isotopes and optical properties to study the biogeochemical process of organic matter (OM), including particulate organic matter (POM) and dissolved organic matter (DOM), which prevents our comprehension of the interactions between POM and DOM in the marine environment. In this study, the origin, distribution, and fate of POM and DOM in Tieshangang Bay, a weak dynamic bay were investigated by measuring δ13C and δ15N of POM, dissolved organic carbon (DOC), and absorption and fluorescence of DOM (CDOM and FDOM). In the upper bay, POM source was mainly originated from terrestrial discharge, whereas the high fluorescence index (FI) indicated that external aquatic organism activity dominated DOM sources. In contrast, in the outer bay, the slightly increased δ13C and enriched δ15N of POM and enhanced fluorescence intensities of protein-like DOM components indicated the considerable contributions of the in situ biological activities to OM. A net addition of DOC and optical components of DOM occurred in both the upper and outer bays. The decomposition of terrestrial POM was responsible for the addition of DOM due to the weak dynamics in the upper bay, whereas the enhanced primary production and the strong decomposition of freshly produced POM jointly contributed to the addition of DOM in the outer bay. Our study suggests that hydrodynamics regulate the biogeochemistry and interactions of POM and DOM in the weak dynamic bay.

Characteristics of Dissolved Organic Matter and Trihalomethane Forming Potential Occurrence in Watersheds with Different Upstream Land Use

Dissolved organic matter (DOM) is the most important natural organic matter (NOM) fraction which reacts with chlorine to form harmful trihalomethanes (THMs) in water bodies. The characteristics of DOM could be affected by land use in the catchment, hence comprehensive study to understand DOM in the water body is important. This study was conducted in two watersheds with different upper stream land use to determine: (1) water characteristics, total organic matter (TOM), and DOM quality and quantity based on optical and absorption properties; (2) fluorescence dissolved organic matter (FDOM) compounds; (3) TOM and DOM relationships; and (4) THMs forming potential (THMFP) in both watersheds. Samples were collected from the upper Cimahi and Cijanggel Rivers which are dominated by settlements and plantations, respectively. Water characteristics were determined by pH, electroconductivity (EC), nitrite, and nitrate in unfiltered and filtered samples. TOM and DOM were characterized by chemical oxygen demand (COD) and chromophoric DOM (CDOM) parameters (A254, A355, A3/4), and organic compounds were determined as FDOM compounds. The measured pH, nitrate, and nitrite in the settlements-impacted watershed were greater than those in the plantations-impacted watershed. The main FDOM compounds in the settlement-impacted river were tryptophan microbial byproduct (T1) and tryptophan aromatic protein (T2), fulvic acid (A), and humic acid (C). Meanwhile, in the plantations-impacted river were T1, A, and C. THMFP was detected in both rivers which were greater in the plantations-impacted watershed than the settlements-impacted watershed.

The removal of dissolved organic matter by marine sponges is a function of its composition and concentration: An in situ seasonal study of four Mediterranean species

Sponges are unique among metazoans in their ability to use dissolved organic matter (DOM), the largest pool of organic matter in the ocean, as a major food source. The effect of variations in DOM abundance and composition on its uptake by sponges has rarely been studied. We examined, in situ, the seasonal uptake of DOM by four sponges [2 species with high microbial abundance (HMA) and 2 with low microbial abundance (LMA)] in the northwestern Mediterranean. Dissolved organic carbon (DOC) showed a strong seasonality with 3-fold higher concentrations in fall-winter (256 ± 16 μmol L−1, mean ± SE) than in spring-summer (88 ± 3 μmol L−1). Dissolved organic nitrogen (DON) showed the opposite trend, with higher summer concentrations (8.9 ± 0.4 μmol L−1) and mean concentrations of 2.5–3.4 μmol L−1 in the other seasons. DOC removal by all sponge species increased linearly with its ambient concentration, but only above a DOC removal threshold that was threefold higher in fall-winter (198 μmol L−1) than in spring-summer (74 μmol L−1). All species showed a concentration-dependent DON removal, but LMA sponges removed more DON than HMA sponges. The DOC removal rate (normalized to sponge volume) was 2–3 times higher in fall-winter, when ambient DOC levels were high, than in spring-summer. Sponges efficiently removed clusters of the fluorescent DOM (FDOM) associated with protein-rich DOM, but not those associated with humic material. The clear threshold for DOC removal and the protein-like FDOM uptake pattern suggest that the quality and quantity of DOM control its removal and transformation by marine sponges. Our results indicate that marine sponges transform the composition of the coastal DOM pool, thereby affecting its fate. It is postulated that the DOM excreted by the sponges is more recalcitrant; consequently, sponge activity enhances carbon sequestration in benthic habitats in a similar fashion to that of the oceanic ‘microbial pump’.

Insights into surface circulation and mixing in James Bay and Hudson Bay from dissolved organic matter optical properties

Hudson Bay and James Bay are fed by numerous rivers, which also deliver large amounts of dissolved organic matter (DOM). The objective of this study is to assess Hudson Bay wide DOM spatial distribution using ultraviolet-visible light absorption and excitation-emission matrix fluorescence spectroscopies. Overall, a five-component PARAFAC model was validated using 1060 discrete samples collected over nine field campaigns between 2009 and 2018 and including the first samples from James Bay ( n = 112). Regional and seasonal variations were observed. Particularly striking was a 9-fold difference in concentration between coastal and marine zones of these bays, which implies limited mixing between those regions. Seasonal variations in absorption coefficient at 355 nm and terrestrial humic-like components were found only in east Hudson Bay, revealing a regional disparity in seasonal DOM behaviour. The summer intensities and relative abundances of DOM revealed that cyclonic circulation transports terrestrial DOM around James Bay following its eastern shores before being transported northward along the western coast of Belcher Islands. The vertical distribution of DOM indicated that fluorescent DOM is delivered to the deeper layer by winter convective mixing in northern Hudson Bay. • Limited mixing between the coastal and marine regions of the bay is observed. • The strong terrestrial signal of east James Bay is found in northern Belcher Island. • DOM is delivered to the deeper layer by winter convection in northern Hudson Bay.

Linking Seasonal Changes in Organic Matter Composition and Nutrients to Shifting Hydraulic Gradients in Coastal Urban Canals

AbstractThe capacity for coastal river networks to transport and transform dissolved organic matter (DOM) is widely accepted. However, climate‐induced shifts in stormwater runoff and tidal extension alter fresh and marine water source contributions, associated DOM, and processing rates of nutrients entering coastal canals. We investigate how time‐variable interactions among coastal water source contributions influence the concentrations of dissolved organic carbon (DOC), nutrients, and DOM composition in urban canals. We quantified the spatiotemporal variability of DOM quality and nutrient concentrations to determine contributions of tidal marine water, rainwater, stormwater runoff, and groundwater to three coastal urban canals of Miami, Florida (USA). We created a Bayesian Monte Carlo mixing model using measurements of fluorescent DOM (fDOM), DOC concentrations, δ18O and δ2H isotopic signatures, and chloride (Cl−). Fractional contributions of groundwater averaged 17% in the dry season and 26% at peak high tide during the subtropical wet season (September–November). The canal‐to‐marine head difference (CMHD) was a primary driver of groundwater contributions to coastal urban canals and monthly patterns of fDOM/DOC. High tide (>1 m) and discharge events were found to connect canals to upstream sources of terrestrial DOM. Loading of terrestrially sourced DOC and DOM is pulsed to urban canals, shunted downstream and supplemented by microbially sourced DOM during the wet season at high tide. Overall, we demonstrate that a combined tracer approach with isotopes and fDOM can help identify groundwater contributions to coastal waterways and that autochthonous fDOM may prime the degradation of carbon or nutrients as the CMHD pushes inland.

Geochemical Features of Ground Ice from the Faddeevsky Peninsula Eastern Coast (Kotelny Island, East Siberian Arctic) as a Key to Understand Paleoenvironmental Conditions of Its Formation

Understanding paleoenvironmental conditions of the permafrost formation allows us to estimate the permafrost carbon pool and its behavior upon thawing in a changing climate. In order to classify different types of ground ice and to reconstruct paleoenvironments, we examined geochemical data of ice wedges (IWs), tabular ground ice (TGI), and lens ice from the eastern coast of the Faddeevsky Peninsula (East Siberian Arctic). We analyzed isotope and ion composition, molecular composition of the gas phase, bulk biogeochemical parameters and dissolved organic matter (DOM) composition in ground ice samples. IWs formed in the Late Pleistocene under the coldest winter conditions and in the Holocene in proximity to the sea. The Holocene IWs have the highest mean d-excess (11–13‰) and a heavier isotope composition by an average of 6‰ compared with the Late Pleistocene IWs. We observe predominance of sea-salt fractions in ion composition of the Holocene IWs, while the Late Pleistocene IW shows enrichment in non-sea-salt component of SO42− (nssSO42−), which is probably associated with mineral leaching of deposits. Higher dissolved organic carbon (DOC) content in the Late Pleistocene IW (to 17.7 mg/L) may indicate more favorable vegetation conditions or lower degree of organic matter mineralization compared to Holocene IWs and TGI. CH4 concentrations were relatively low with a maximum value of 2.27 μmol/L. DOM composition, supposed to record the paleoenvironment of the freezing process, was for the first time tried as a biomarker for paleoenvironmental reconstructions of ground ice formation. Parallel factor (PARAFAC) analysis of EEM (Excitation-Emission matrix) of fluorescent DOM decomposes four components: P1–P3, which are related to allochthonous humic-like constituents, and P4, which is relevant to autochthonous fraction associated with microbial activity. The distribution of fluorescent DOM tracked the variability in both paleoclimate conditions of the IW formation (discriminating the Holocene and the Late Pleistocene IWs) and types of ground ice (IW and TGI), which demonstrates the potential of the used approach.

Land use impact on the levels of fluorescent dissolved organic matter, phytoplankton and zooplankton in urban lakes

Urban lakes are vulnerable ecosystems, sensitive to environmental challenges, such as pollution, land use transformation and climate change. Closed and open lakes play relatively different roles in the accumulation, transport and transformation of pollutants and organic matter. Land use can influence the concentration of dissolved organic matter and the abundance of phytoplankton. Little is known about the relationship between fluorescent dissolved organic matter (FDOM), phytoplankton and zooplankton in open and closed lakes, relative to the impact of land use. This study aims to determine the connection between various types of land use and FDOM characteristics, as well as phytoplankton and zooplankton abundances in urban lakes. For the closed lakes samples, results showed positive associations between Bacillariophyceae and Testacea, and the protein-like fraction, while for open lakes, positive associations were found between these groups and the microbial humic-like fraction. Also, copepods and rotifers were associated with the humic-like fraction, in closed lakes, but in open lakes copepods correlated with the biological index, and rotifers with the humification index and fluorescence T/C ratio. Results suggested that discontinuous urban fabric, dump sites and abandoned lands decreased the abundance of protein-like fraction and phytoplankton. However, lakes with the highest quantity of protein-like FDOM also had the highest coverage of continuous urban fabric around the lake. Green urban areas decreased the quantity of humic-like FDOM. No impact by land use type was observed on zooplankton groups, suggesting that zooplankton may be less vulnerable to land use. Our findings will contribute to an improved urban water management and to an effective control of FDOM and phytoplankton abundances in urban lakes.

Seasonal variations in dissolved organic matter concentration and composition in an outdoor system for bank filtration simulation

Dissolved organic matter (DOM) in surface waters can vary markedly in character depending on seasonal variations such as rainfall intensity, UV radiations and temperature. Changes in DOM as well as temperature and rainfall intensity over the year can affect the biochemical processes occurring in bank filtration (BF). Identification and characterization of DOM in the surface water could help to optimize the water treatment and provide stable and safe drinking water. This study investigated year-long variations of DOM concentrations and compositions in a surface water of a circulated outdoor pond (research facility) connected to a BF passage. DOM was dominated by humic substances and a changing pattern of DOM in surface water was observed throughout the year. A significant increase of DOM (∼ 38%) in surface water was noted in August compared to November. The fluorescent DOM showed that DOM in summer was enriched with the degradable fraction whilst non-degradable fraction was dominated in winter. A constant (1.7 ± 0.1 mg/L) effluent DOM was recirculated in the system throughout the year. DOM removal through BF varied between 4% to 39% and was achieved within a few meters after infiltration and significantly correlated with influent DOM concentration (R2 = 0.82, p < 0.05). However, no significant (p > 0.05) change in the removal of DOM was observed in two subsurface layers (upper and lower). This study highlights the presence of a constant non-degradable DOM in the bank filtrate, which was not affected by temperature, redox conditions and UV radiations.

Seasonal and diel modulation of DOM in a mangrove-dominated estuary.

Rivers and estuaries are the main links between continents and oceans. The Paraíba do Sul River is among the most important rivers of the southeastern Brazilian region, carrying an average of 0.08 Tg of dissolved organic matter (DOM) to the ocean but has been facing significant changes in river discharge. In this study, we aimed to provide insights into the sources and transformations of chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) sources across a salinity gradient under changing river discharge scenarios. Three spatial surveys were performed covering the entire salinity gradient of the main estuarine channel and surrounding mangrove waters under contrasting river discharge (178 to 1240 m3 s-1), and diel sampling was conducted in the mangrove tidal creek. The characterization of DOM through the parallel factor analysis (PARAFAC) model identified six components across the river-ocean gradient and mangrove creek: terrestrial origin (C1 - fulvic acid and C2 and C3 - humic-like), protein-like (C4), tryptophan-like (C5), and tyrosine-like (C6). Our results showed a shift in DOM composition and contribution along the salinity gradient, from terrestrial (C3) to autochthonous (C5 and C6) signatures. The October-17 dry campaign was characterized by a higher proportion of microbial protein-like component C4 and a lower contribution of humic-like components compared to February-17 and March-18 across the salinity gradient with an increase in the mixing zone. The DOM compositions of the February 17 dry and March 18 wet campaigns were similar. Additionally, the March-18 wet campaign, marked by the highest river discharge, showed higher inputs of terrestrial DOM (C1-C3 components) compared to February-17 in the estuary, which allowed DOM to be transported rather than transformed. The mangrove diel study showed that tidal fluctuations are also an important driver of carbon input to the mangrove creek with a possible impact on DOM composition in estuarine waters.

Evaluating the pH-dependence of DOM absorbance, fluorescence, and photochemical production of singlet oxygen.

The protonation state of dissolved organic matter (DOM) impacts its structure and function in natural and engineered environmental systems, including DOM's ability to absorb light and form photochemically produced reactive intermediates (PPRI). However, the impacts of pH on DOM optical properties and PPRI formation have largely been evaluated separately, with less information being available on their interrelationship as a function of pH for the same set of samples. It is also unclear whether the impact of pH on optical spectra and associated optical surrogates for molecular size (e.g., E2 : E3) of DOM isolates is representative of the behavior of whole water samples. To address these knowledge gaps, spectral pH titrations were performed for seven humic substance and natural organic matter isolates, three whole water samples, and three model compounds. Comparison of the fractional and differential absorption and fluorescence spectra between DOM isolates, whole water samples, and model compounds revealed similar spectral features between all samples. The results show that spectral features observed for DOM isolates also occur for whole water samples, which suggests that there is overlap in the types of chromophores present in DOM isolates and whole waters. Although results from model compounds overlapped with DOM, especially in the ultraviolet region of the spectrum, no model compound replicated DOM's pH dependence perfectly. By measuring apparent quantum yields of singlet oxygen (ΦΔ), we show that aquatic DOM isolates exhibit a different pH-dependence (ΦΔ ∝ pH-1) than soil-derived humic acid isolates (ΦΔ ∝ pH). For aquatic DOM isolates, ΦΔ values measured at different pH were not correlated to apparent fluorescence quantum yields (Φf), suggesting that pH impacts singlet and triplet excited state DOM dynamics in different ways. In contrast, the proportional relationship between Φf and ΦΔ with increasing pH for soil humic acid isolates suggests that pH impacts singlet and triplet excited DOM in these samples in a similar fashion.

Remote sensing of fluorescent humification levels and its potential environmental linkages in lakes across China

The pollution or eutrophication affected by dissolved organic matter (DOM) composition and sources of inland waters had attracted concerns from the public and government in China. Combined with remote sensing techniques, the fluorescent DOM (FDOM) parameters accounted for the important part of optical constituent as chromophoric dissolved organic matter (CDOM) was a useful tool to trace relative DOM sources and assess the trophic states for large-scale regions comprehensively and timely. Here, the objective of this research is to calibrate and validate a general model based on Landsat 8 OLI product embedded in Google Earth Engine (GEE) for deriving humification index (HIX) based on EEMs in lakes across China. The Landsat surface reflectance was matched with 1150 pairs fieldtrip samples and the nine sensitive spectral variables with good correlation with HIX were selected as the inputs in machine learning methods. The calibration of XGBoost model (R2 = 0.86, RMSE = 0.29) outperformed other models. Our results indicated that the entire dataset of HIX has a strong association with Landsat reflectance, yielding low root mean square error between measured and predicted HIX (R2 = 0.81, RMSE = 0.42) for lakes in China. Finally, the optimal XGBoost model was used to calculate the spatial distribution of HIX of 2015 and 2020 in typical lakes selected from the Report on the State of the Ecology and Environment in China. The significant decreasing of HIX from 2015 to 2020 with trophic states showed positive control of humification level of lakes based on the published document of Action plan for prevention and control of water pollution in 2015 of China. The calibrated model would greatly facilitate FDOM monitoring in lakes, and provide indicators for relative DOM sources to evaluate the impact of water protection measures or human disturbance effect from Covid-19 lockdown, and offer the government supervision to improve the water quality management for lake ecosystems.

Temperature effects on microbial dissolved organic matter metabolisms: Linking size fractions, fluorescent compositions, and functional groups

This study elucidated the compositional and structural variations of size fractions of microbially-induced dissolved organic matter (DOM) caused by short-term temperature changes (5 to 35 °C), taking riverine DOM as an example. A simple and efficient method combining fractionation-[parallel factor analysis and two-dimensional Fourier-transform infrared correlation spectroscopy (PARAFAC-2D FTIR COS)]-correlation was introduced to link fluorescent DOM components and their structures in terms of surface functional groups. Results indicated that the higher temperature stimulated the decomposition of aromatics (sizes decreased from 10 kDa-0.22 μm to <10 kDa) and the transformation of proteins to humics (with sizes <0.22 μm); while both the higher and lower temperatures inhibited the utilization of larger-sized DOM (>0.22 μm, especially the non-fluorescence part) and synthesis of larger-sized microbial-derived proteins and humics (>0.22 μm), which may result in more smaller-sized (<10 kDa) and refractory aromatics transported from rivers to oceans in the warming future. However, the structure-determined DOM behaviors could be less affected by temperature since the fluorescent proteins and humics revealed similar functional group compositions, such as carboxyl, hydroxyl, carbonyl/aldehyde, carboxylic anhydride, and carboxamide groups. These findings have strong implications for DOM biogeochemistry in future temperature-shock scenarios. The proposed method will support in-depth analyses of structure-regulated processes from a mechanistic perspective.

Fluorescence Quenching of Humic Substances and Natural Organic Matter by Nitroxide Free Radicals.

Fluorescence spectroscopy is one of the most frequently used techniques for studying dissolved organic matter (DOM) in natural and engineered systems. However, the spatial distribution and fluorophores, including local and interacting states, within DOM's larger structure remains poorly understood. In this study, we used two nitroxide fluorescence quenchers to evaluate the chemical and spatial heterogeneity of DOM fluorophores. Several results from quenching experiments with cationic 4-amino-TEMPO (tempamine), including downward-curving Stern-Volmer plots and spectral dependent quenching, show that multiple emitting species contribute to the observed emission even at a single excitation wavelength. Furthermore, for DOM isolates of diverse geographic origins (soil vs aquatic) and isolation procedures (reverse osmosis vs humic substances), the maximum extent of quenching occurs on the red edge of the emission spectra. For soil humic substance isolates, the spectral dependent quenching was significant enough to affect a blue shift in the average emission wavelength. The same soil humic substance isolates whose emission spectra were blue shifted by tempamine quenching were also blue shifted by decreasing solution pH and decreasing solvent polarity, which suggests a role for anionic fluorophores (e.g., hydroxybenzoic acids) in long wavelength fluorescence. Finally, curvature in Stern-Volmer plots indicate that between 10 and 50% of emitting species detected by steady-state fluorescence are inaccessible to quenching by tempamine, suggesting that this fraction of fluorophores may be inaccessible to water solvent. Results from this study provide an assessment of the spatial distribution of fluorophores within DOM and help to reconcile prior studies on the role of solvent polarity and pH on DOM fluorescence.

Optical variations of dissolved organic matter due to surface water - groundwater interaction in alpine and arid Datonghe watershed

The direction and quantity of surface water - groundwater interaction (SGI) in alpine-arid zones can be tracked using multiple tracers. However, few studies have examined whether the optical indices of dissolved organic matter (DOM) can also track SGI. This study used excitation-emission matrix spectroscopy combined with parallel factor analysis (EEM-PARAFAC) to reveal the optical variations in dissolved organic matter (DOM) in groundwater and surface water with various SGIs in the Datonghe watershed. The results showed that the absorbance spectral indices of DOM did not vary with SGI, whereas DOM fluorescence varied with SGI. PARAFAC indicated that groundwater predominantly recharged by precipitation had significantly lower humic-like (C2 and C3) fluorescence than groundwater predominantly recharged by riverine water. Since humic-like substances were more likely to be retained in the aqueous phase than protein-like substances, significantly fewer protein-like substances (C4) were introduced when surface water was recharged to groundwater. This suggests that C4 can be used as an effective indicator to identify the SGI process from surface water to groundwater. Based on the principal component analysis of DOM and hydrochemical indicators, it was concluded that traditional chemical tracers were significantly and positively correlated with humic-like substances C2 and C3. Given that C3 is more stable and persistent in the environment, it could be used to track SGI processes midstream of the watershed. The findings of this study will assist in accurately identifying the processes and mechanisms of SGI on a regional scale and provide a basis for future water resource management and the protection of water ecosystems.

Effects of acid mine drainage on photochemical and biological degradation of dissolved organic matter in karst river water

Dissolved organic matter (DOM) can be removed or transformed by photochemical and biological processes, producing the negative effect of transforming organic carbon into inorganic carbon, which plays a vital role in the karst carbon cycle. However, acid mine drainage (AMD) will affect this process, so the degradation of DOM in karst river water (KRW) needs to be studied in this context. In this study, to reveal the evolution processes of DOM under photochemical and biological conditions in AMD-impacted KRW, AMD and KRW were mixed in different ratios under conditions of visible light irradiation (VL), biodegradation (BD), ultraviolet irradiation (UV) and ultraviolet irradiation + biodegradation (UV+BD). The average DOC concentrations in samples after mixing AMD and KRW in different proportions decreased significantly (by 23%) in UV+BD, which was 1.2–1.4 times higher than under the other conditions and would lead to a significant release of inorganic carbon. Further analysis of the fluorescence parameters via parallel factor analysis (PARAFAC) revealed that the DOM fluorescence components in AMD comprised mainly protein-like substances derived from autochthonous components, while the DOM fluorescence components in KRW were mainly humic-like substances with both autochthonous and allochthonous sources. Therefore, AMD could promote both the photochemical and biological degradation of DOM in karst receiving streams, resulting in the conversion of DOC to inorganic carbon. The results showed that the synergistic effects of UV+BD and AMD accelerated the degradation of DOM and the release of inorganic carbon in KRW, thus affecting the stability of the karst carbon cycle.

Using fluorescence index (FI) of dissolved organic matter (DOM) to identify non-point source pollution: The difference in FI between soil extracts and wastewater reveals the principle

Traceability and quantification of agricultural non-point source pollution are of great significance to water pollution management in watersheds. In this study, fluorescence components and indices of dissolved organic matter (DOM) in the river, wastewater and soil extracts from different land use types were analyzed to screen indicators that can identify non-point source pollution in 15 independent small watersheds located at the southern Qinling piedmont (China). The results showed that DOM fluorescence components in soil extracts among different land uses didn't have significant differences. The values of humification index (HIX) did not vary obviously between soil extracts and wastewater, with the mean values ranging from 3.4 to 3.9. However, the average value of fluorescence index (FI) of effluent wastewater was about 2.1 and did not change significantly through treatment. The FI values of soil extracts were generally between 1.5 and 1.7. The FI values in most river waters were just between the FI values of wastewater and soil extracts. This phenomenon indicated that FI could be used as an indicator to distinguish point source and non-point source pollution. Besides, the correlation analysis showed a significant positive relationship between the non-point source pollution calculated by FI and δ15N. The relationship was different in January and July, but further confirmed the reliability of using FI to quantify non-point source pollution. This study demonstrated the feasibility of using FI to identify non-point source pollution. When combined with handheld fluorescence spectrometers and unmanned aerial vehicle-mounted fluorescence spectrometers, this method may be adopted more widely.