Anthropogenic Dissolved Organic Matter Research Articles

Anthropogenic dissolved organic matter accumulation fuels greenhouse gas diffusive emissions in urban lakes along trophic state levels

Lakes are an important reservoir of dissolved organic matter (DOM) and also emit large amounts of greenhouse gases (GHGs), such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Yet, the linkages between quantity and quality of DOM and GHGs emissions are still not well understood. Hence, we investigated how DOM optical properties mediated dissolved GHGs levels and diffusive fluxes along a trophic state level in subtropical urban lakes, China. Our study showed that anthropogenic protein-like DOM (tryptophan- and tyrosine-like components) dominated the DOM pools, comprising 62% of total fluorescence DOM (FDOM). Partial least squares path modeling (PLS-PM) showed that the direct contribution of relative abundance of DOM to CO2 and CH4 diffusion in the highly-eutrophic state was higher than in the mesotrophic and lightly/moderately-eutrophic states. In particular, protein-like DOM primarily accounted for CO2 variations (44%-49%), while humic- and protein-like DOM contributed comparably to CH4 variations (38%-40% vs. 36%-40%). Furthermore, in the lightly/moderately- and highly-eutrophic states, nutrients contributed to DOM, CO2 and CH4 in both direct and indirect ways, while phytoplankton (chlorophyll a, Chl-a) negatively and directly affected carbon emissions. However, only nitrogen content directly contributed to N2O production and diffusion in the mesotrophic and lightly/moderately-eutrophic states. We concluded that protein-like DOM enrichment had the potential to trigger CO2 and CH4 diffusion and this process was largely mediated by nutrient levels. N2O diffusion was found to be mainly influenced by nitrogen loadings and forms. Our findings highlight the urgency for effective strategies to reduce anthropogenic DOM inputs and control nutrient levels to reduce GHGs diffusion in highly human-impacted aquatic systems.

Natural and anthropogenic dissolved organic matter in landfill leachate: Composition, transformation, and their coexistence characteristics

A large number of natural and anthropogenic wastes were landfilled, and dissolved organic matter (DOM) were formed during landfill. However, the composition, transformation, and coexistence characteristics of natural and anthropogenic DOM in leachate remain unclear. Fourier transform ion cyclotron resonance mass spectrometry, size exclusion chromatography, gas chromatography coupled with mass spectrometry, and three-dimensional excitation-emission matrix spectrum were employed to clarify comprehensively the abovementioned question. The results showed that natural DOM in young leachate constituted mainly straight-chain organic acids, protein substances, and building blocks of humic substances (BB). Straight-chain organic acids vanished in old leachates, and the concentration of protein substances and BB decreased from 44% to 26% and from 47% to 12%, respectively, while CHON and CHONS were degraded to CHO and CHOS during the process. As to anthropogenic DOM, its types and relative content in leachate increased during landfill, and aromatic acids, terpenes, halogenated organics, indoles, and phenols became the main organic components in old leachate. Compared to natural DOM, anthropogenic DOM was degraded slowly and accumulated in leachate, and some of the natural DOM facilitated the dechlorination of dichlorinated organic compounds. This study demonstrates that landfill led to an increase in humic substances and halogenated organic compounds in old leachate, which was intensified with concentrated leachate recirculation.

Short-term photodegradation of autochthonous and allochthonous dissolved organic matter in Lake Taihu, China.

Photochemistry is one of the key processes that shape the quality of dissolved organic matter (DOM) in aquatic systems, yet the photoreactivity of DOM from different sources remains largely unclear. In this study, DOM from 10 typical autochthonous and allochthonous sources in Lake Taihu basin were exposed to simulated sunlight, and quantitative and compositional changes of the DOM were explored by measuring its UV-Visable absorption and fluorescence spectroscopy. Photochemical release of nutrients was also explored during the incubations. Results showed that, although DOM from most sources experienced photobleaching effects with decreased absorption coefficients at254 nm (a(254)) and fluorescencecomponent intensities after light exposure, photochemical alterations of DOM linked to their original composition. Macrophyte-derived (Potamogeton malaianus) DOM, with the largest molecular size, showed increased a(254), humic- andprotein-like fluorescence component(C1 and C2)abundances, and inorganic nutrient concentrations relative to dark controls, indicating photo-release of labile components. However, DOM with relatively higher aromaticity, e.g., fromagricultural water and the lake, showed photobleaching effects and increased humification degree, probably due to the loss of aromatic components. Allochthonous anthropogenic DOM, e.g., from sewage, showed stronger photo-ammonification, likely relating to the fresh labile N-containing compositions. The form of inorganicnutrient releases during theDOM photolysis also varied with the original DOM sources. Macrophyte-derived DOM incubations showed larger photo-releases of NO3- and PO43-, while NO2- dominated inorganicnutrient releases during groundwater DOM lightincubations. Thus, this study concludes that the photoreactivity of DOM closely relates to its original composition and sources.

Distinguishing between Sources of Natural Dissolved Organic Matter (DOM) Based on Its Characteristics

Increasing levels of dissolved organic matter (DOM) in watercourses in the northern hemisphere are mainly due to reduced acid rain, climate change, and changes in agricultural practices. However, their impacts vary in time and space. To predict how DOM responds to changes in environmental pressures, we need to differentiate between allochthonous and autochthonous sources as well as identify anthropogenic DOM. In this study we distinguish between allochthonous, autochthonous, and anthropogenic sources of DOM in a diverse watercourse network by assessing effects of land cover on water quality and using DOM characterization tools. The main sources of DOM at the studied site are forests discharging allochthonous humic DOM, autochthonous fulvic DOM, and runoff from urban sites and fish farms with high levels of anthropogenic DOM rich in protein-like material. Specific UV absorbency (sUVa) distinguishes allochthonous DOM from autochthonous and anthropogenic DOM. Anthropogenic DOM differs from autochthonous fulvic DOM by containing elevated levels of protein-like material. DOM from fishponds is distinguished from autochthonous and sewage DOM by having high sUVa. DOM characteristics are thus valuable tools for deconvoluting the various sources of DOM, enabling water resource managers to identify anthropogenic sources of DOM and predict future trends in DOM.

Innovative approach to reveal source contribution of dissolved organic matter in a complex river watershed using end-member mixing analysis based on spectroscopic proxies and multi-isotopes

Dissolved organic matter (DOM) in river watersheds dynamically changes based on its source during a monsoon period with storm event. However, the variations in DOM in urban and rural river watersheds that are dominated by point and non-point sources have not been adequately explored to date. We developed an innovative approach to reveal DOM sources in complex river watershed systems during pre-monsoon, monsoon, and post-monsoon periods using end-member mixing analysis (EMMA) by combining multi-isotope values (δ13C-DOC, δ15N-NO3 and δ18O-NO3) and spectroscopic indices (fluorescence index [FI], biological index [BIX], humification index [HIX], and specific UV absorbance [SUVA]). Several potential end-members of DOM sources were collected from watersheds, including top-soils, groundwater, plant group (fallen leaves, riparian plants, suspended algae), and different effluents (cattle and pig livestock, agricultural land, urban, industry facility, swine treatment facility and wastewater treatment facility). Concentrations of dissolved organic carbon, dissolved organic nitrogen, NO3-N, and NH4-N increased during the monsoon period with an increase in the input of anthropogenic DOM, which have higher HIX values owing to the flushing effect. The results of EMMA indicate that soil and agricultural effluents accounted for a substantial contribution of anthropogenic DOM at varying rates based on seasons. We also found that results of EMMA based on combining spectroscopic indices and δ13C-DOC isotope values were more accurate in tracing DOM sources with respect to land-use characteristics compared to applying only spectroscopic indices. The positive relationship between FI, BIX and δ15N-NO3 were revealed that nitrate would be decomposed from DOM affected by intensive agricultural activities. In addition, consistent with the EMMA results, the molecular composition of the DOM was clearly evidenced by a large number of CHON formulas, accounting for over 50% of the total characterized compounds, including pesticides and pharmaceuticals used in agriculture farmland and livestock. Our results clearly demonstrated that EMMA based on combing multi-stable isotopes and spectroscopic indices could be trace the DOM source, which is important for understanding changes in the DOM quality, and application of nitrate isotopes and molecular analysis supports in-depth interpretation. This study provides easy and intuitive techniques for the estimation of the relative impacts of DOM sources in complex river watersheds, which can be verified in various ways rather than relying on a single technique approach.

Quantification of groundwater versus fish-farm sources of nutrients in the coastal water off Jeju Island, Korea, using fluorescent dissolved organic matter as a tracer

The concentrations of nutrients and dissolved organic matter (DOM) in the coastal waters off Jeju Island, Korea, are known to be influenced mainly by submarine groundwater discharge (SGD) and fish-farm effluents, in addition to the background open-ocean seawater from the Tsushima Current. However, the differentiation of the effect of fish-farm effluents from SGD is very challenging since most of the farms in this island utilize groundwater as a rearing water. Thus, in this study, we measured the concentrations of nutrients and fluorescent DOM (FDOM) in seawater, fresh groundwater (FGW), and farm water in two coastal areas off Jeju Island, in May and August 2021, in order to determine the effect of SGD versus fish-farm effluents. The results showed that humic-like FDOM (FDOMH) and NH4+ concentrations were greatly enriched owing to organic matter decomposition in the farm waters. We used FDOMH, as a tracer for the farm effluent. The end-member mixing model for FDOMH and salinity showed that FGW contributed about 73% of NO3− (avg. 17 ± 20 μM), whereas the farm effluent contributed about 95% of NH4+ (avg. 5.6 ± 4.1 μM) and 71% of FDOMH (avg. 0.86 ± 0.49 R.U.) in the coastal waters. Thus, our result shows that fish-farm effluents can be an important source of anthropogenic DOM and nutrients in coastal waters, where farms are being operated intensively.

Characteristics, Sources, and Seasonal Variability of Dissolved Organic Matter (DOM) in the Ganges River, Bangladesh

This study investigated seasonal variability of sources and fluorescence characteristics of dissolved organic matter (DOM) in the Ganges River using three-dimensional excitation-emission matrix (3DEEM) spectroscopy and parallel factor analysis (PARAFAC). 3DEEM and PARAFAC identified five fluorophores (Peak: A, C, M, T, W) and four fluorescent components, i.e., detergent, fulvic acid (M-type), fulvic acid (C-type), and protein-like, respectively, showing high fluorescence characteristics in the pre-monsoon (March-June) and monsoon (July-October) compared to the post-monsoon (November-February) period. Dissolved organic carbon (DOC) and Specific ultraviolet absorbance (SUVA254) were in the range 1.85-4.7 mg/L and 1.23-5.51 L/mg-m, respectively. DOM components were both fresh and microbial-derived throughout the year. Local hydrological and physicochemical conditions supported the autochthonous and aromatic DOM production in post-monsoon, and richness of terrestrial-derived natural and anthropogenic DOM in the pre-monsoon and monsoon periods. The molecular weight of DOM decreased from the mid of pre-monsoon and continued till monsoon with the increase of terrestrial-derived DOM and photo-irradiation as well as microbial activity. Tryptophan-like fluorescence (TLF) showed high intensity throughout the peak-flow pre-monsoon and monsoon periods, demonstrating a high to intermediate risk of microbial contamination of the Ganges River. The seasonal variability of DOM characteristics suggests that the source and biogeochemistry of DOM in the Ganges Rivers might be sensitive to local hydrology and climate. • DOC concentrations and DOM fluorescence intensity attained their highest values at the beginning of monsoon and showed high seasonal variability. • The compositions of DOM carried by the Ganges River varied at different times of the year, and fresh, autochthonous and less aromatic DOM dominated in the late pre-monsoon and monsoon. • PARAFAC model identified four fluorescent DOM components (detergent-, fulvic- (M like), fulvic- (C like) and protein-like) which showed high seasonal variability with rainfall and river discharge.

Determining the leading sources of N-nitrosamines and dissolved organic matter in four reservoirs in Southern China

The presence of carcinogenic N-nitrosamines and dissolved organic matter (DOM) in freshwater is a significant concern from the perspective of public health and drinking water treatment plant operation. This study investigated the N-nitrosamines concentration and their precursors' distributions, and DOM composition in four reservoirs located in a southern city of China. A total of 22 renowned precursors were identified. Precursors from industrial and pharmaceutical origins were found to be dominant in all reservoirs; however, traces of pesticide-based precursors, i.e. pirimicarb and cycluron were also found. The distribution of nine N-nitrosamines was substantially different among the reservoirs. N-Nitrosodibutylamine (NDBA), N-Nitrosopiperidine (NPIP), N-Nitrosodimethylamine (NDMA), and N-Nitrosopyrrolidine (NPYR) were abundantly present in all reservoirs. Most of N-nitrosamines except NDMA and N-nitrosodiethylamine (NDEA) were far below the generally accepted cancer risk of 10−6, and NDMA/NDEA were found close to the risk level (10−6). Anthropogenic DOM was dominant in three reservoirs as depicted by a higher biological index (BIX) than the humification index (HIX). By the principle component analysis, BIX appeared as an indicator of N-nitrosamines (except NDEA and NPIP). A strong and direct relationship was observed between the NDMA-formation potential (FP) and concentration of total N-nitrosamines (∑NA), and BIX. These results confirmed that the anthropogenic activities were the leading source of DOM and N-nitrosamines in this city based on land-use.

Assessment of contamination by anthropogenic dissolved organic matter in the aquifer that underlies the agricultural area.

The use of wastewater for agricultural irrigation is a common practice worldwide; long-term use of wastewater can have adverse effects, such as the migration of the anthropogenic dissolved organic matter into the aquifer. Three-dimensional fluorescence spectroscopy (EEM) was used to investigate the characteristics of dissolved organic matter (DOM) in groundwater and irrigation wastewater, to establish the effect of intensive irrigation on the water quality from the aquifer that underlies the area. The fluorescence spectra showed the presence of humic and fulvic acids and anthropogenic organic compounds similar to aromatic proteins and soluble microbial products in wastewater resources. The significant fraction of DOM in groundwater samples are aromatic proteins and soluble microbial products, identical to wastewater. Chlorides and nitrate ion concentrations suggest a local flow system. High levels of TDS are associated with intensive irrigation with residual water and the return irrigation associated with a gradual increase in salts of CO32-, NO3-, HCO3-, Cl-, and SO42-. The anthropogenic DOM is a useful indicator of water quality management in groundwater based on origin tracking of DOM and changes in organic pollutants. Fluorescence spectroscopy can be used to investigate groundwater pollution characteristics and monitor DOM dynamics in groundwater.

High Anthropogenic Organic Matter Inputs during a Festival Increase River Heterotrophy and Refractory Carbon Load.

Streams and rivers metabolize dissolved organic matter (DOM). Although most DOM compounds originate from natural sources, recreational use of rivers increasingly introduces chemically distinct anthropogenic DOM. So far, the ecological impact of this DOM source is not well understood. Here, we show that a large music festival held adjacent to the Traisen River in Austria increased the river’s dissolved organic carbon (DOC) concentration from 1.6 to 2.1 mg L–1 and stream ecosystem respiration from −3.2 to −4.5 mg L–1. The DOC increase was not detected by sensors continuously logging absorbance spectra, thereby challenging their applicability for monitoring. However, the fluorescence intensity doubled during the festival. Using parallel factor analysis, we were able to assign the increase in fluorescence intensity to the chemically stable UV-B filter phenylbenzimidazole sulfonic acid, indicating organic compounds in sunscreen and other personal care products as sources of elevated DOC. This observation was confirmed by liquid chromatography coupled with mass spectrometry. The elevated respiration is probably fueled by anthropogenic DOM contained in beer and/or urine. We conclude that intense recreational use of running waters transiently increases the anthropogenic DOM load into stream ecosystems and alters the fluvial metabolism. We further propose that chemically distinct, manmade DOM extends the natural range of DOM decomposition rates in fluvial ecosystems.

Assessment of C-DBP and N-DBP formation potential and its reduction by MIEX® DOC and MIEX® GOLD resins using fluorescence spectroscopy and parallel factor analysis

This study investigated the applicability of parallel factor analysis (PARAFAC) of fluorescence excitation-emission matrices (EEM) spectra to assess the formation potentials (FP) of carbonaceous and nitrogenous disinfection byproducts (C-DBP and N-DBP) and the FP reduction by the magnetic ion exchange resins, MIEX® DOC and MIEX® GOLD. Two source waters of different nature — a surface water and a secondary treated wastewater effluent — were studied. The samples were analyzed for formation potentials of trihalomethanes (THM4), haloacetonitriles (HAN4), haloketones (HK2), and chloropicrin (CPN). A 4-component PARAFAC model was developed from 150 EEM samples generated from the raw source waters and their treatment with MIEX® resins. Components C1, C2, and C3 corresponded to humic-like dissolved organic matter (DOM) while C4 corresponded to protein-like DOM. Both MIEX® resins preferentially removed components C1, C2, and C3 over C4, indicating affinity with humic materials. MIEX® resins were shown to be more effective to treat surface water than secondary effluent, including effective removal of DBP precursors with extended bed volume treatment. Among all parameters investigated, THM4-FP strongly correlated with humic-like component C3, while HAN4-FP strongly correlated with protein-like component C4 (ρ > 0.89 and p < 0.01); CPN-FP and HK2-FP both correlated with anthropogenic DOM C2 (ρ > 0.89 and p < 0.01). Our results indicate that EEM–PARAFAC was valuable for assessing DBP formation potentials and removal of their precursors by MIEX® resins in different water sources.

Molecular composition and spatial distribution of dissolved organic matter (DOM) in the Pearl River Estuary, China

Environmental contextEstuaries play an important role in global carbon cycling in terms of transforming dissolved organic matter (DOM). We describe the molecular composition and spatial distribution of DOM in the Pearl River Estuary, an area severely impacted by anthropogenic activities, and show how DOM composition gradually changes with salinity. The results will help our understanding of the sources and transformations of anthropogenic DOM discharged to the coastal seas. AbstractThe Pearl River is the second-largest river in China in terms of water discharge and brings enormous amounts of nutrients and terrestrial organic matter to the South China Sea, which makes the Pearl River Estuary (PRE) highly eutrophic. However, the molecular composition and distribution of dissolved organic matter (DOM) in the PRE have scarcely been investigated. In this study, solid-phase extraction (SPE) was performed to collect DOM samples from PRE along a salinity gradient. The samples were characterised by negative-ion electrospray ionisation (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to analyse their molecular composition and spatial distribution. The FT-ICR MS results showed that the terrestrial organic matter was gradually diluted and/or degraded during the migration from the river to the coastal ocean. Furthermore, both sulfur containing and unsaturated molecules were highly abundant in the upper stream samples, which indicated that anthropogenic input might be another important source of the assigned DOM in PRE. A group of bio-refractory molecules, characterised as carboxylic-rich alicyclic-like molecules, was found to accumulate with the increase of salinity. The composition of the SPE-DOM showed a gradual variation with the salinity and spatial changes; however, the variation was slightly different from those in pristine estuaries. This study demonstrates that the molecular composition of DOM is crucial for elucidating its source and transformation in an estuary.

Synergistic effects of urban tributary mixing on dissolved organic matter biodegradation in an impounded river system

Dams and wastewater may greatly perturb riverine fluxes of dissolved organic matter (DOM) and CO2, yet little is known about the relationships between altered DOM quality and CO2 emission in eutrophic impounded river systems. A basin-wide field survey of surface water CO2 and dissolved organic carbon (DOC) was combined with laboratory incubations to examine how dams and urban tributaries delivering treated wastewater influence longitudinal patterns in DOM properties and CO2 along the impounded Han River traversing Seoul metropolitan area. Fluorescent DOM indices including parallel factor analysis (PARAFAC) components were used to characterize DOM in relation to biodegradable DOC (BDOC). Compared with distinct downstream increases in DOC and CO2, BDOC concentration and its proportion in DOC (%BDOC) were highly variable along the mainstem and peaked at urban tributaries. Longitudinal increases in fluorescence index (FI), biological index (BIX), and two PARAFAC components (C2 and C3) contrasted with general decreases in humification index (HIX) and C1, reflecting increasing downstream inputs of anthropogenic DOM. During a 5-day incubation employing continuous CO2 measurements, the cumulative production of CO2 in the mainstem water mixed with urban tributary water was significantly higher than the level expected for conservative mixing of the two samples, indicating a synergistic enhancement of DOM biodegradation. Molecular formulas identified by Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) revealed more consumed molecules in the mainstem water and more newly produced molecules in the tributary water over the 5-day incubation, implying abundant labile components in the mainstem water discharged from the upstream dam and highly processed tributary DOM limited in immediately biodegradable organic materials. Downstream increases in CO2 and DOC along the Han River, combined with the synergistic effect observed in the mixed water, suggest that mixing wastewater-derived DOM with labile autochthonous DOM can enhance CO2 production in the river system perturbed by impoundment and wastewater.

Molecular transformation of natural and anthropogenic dissolved organic matter under photo-irradiation in the presence of nano TiO2

Photochemical transformation of dissolved organic matter (DOM) plays a very important role in the cycling of organic carbon in aquatic systems. Increasing release of photoactive nanoparticles such as titanium dioxide nanoparticles (nano TiO2) into surface water may impact this process. The present study employed Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to examine the molecular transformation of natural DOM (peat DOM, DOMp) and anthropogenic DOM (sludge-derived DOM, DOMs) under photo-irradiation as affected by nano TiO2. Differences in molecular components between DOMp and DOMs were observed. DOMs contained more heteroatom formulas (76%) with low aromaticity and low carbon oxidation state than did DOMp (22%). The presence of nano TiO2 resulted in significant decreases in both DOM content and molecular diversity under photo-irradiation. Consistent alterations were observed between DOMp and DOMs such that high molecular weight compounds, high aromaticity and/or heteroatom S-containing compounds were more easily photodegraded in the presence of nano TiO2; whereas the average carbon oxidation state decreased in DOMp but increased in DOMs, likely due to the significant differences in O abundance, especially in the contents of carboxyl moieties, between DOMp and DOMs. The findings of the present study suggest that the release of nano TiO2 into aquatic environment will accelerate the consumption of dissolved organic carbon and the attenuation of molecular diversity for both DOM in waters.

Tracing dissolved organic matter (DOM) from land-based aquaculture systems in North Patagonian streams

Chile is the second largest producer of salmonids worldwide. The first step in the production of salmonids takes place in land-based aquacultures. However, the effects of the discharge from these aquacultures on stream dissolved organic matter (DOM) content, molecular composition and degradability are unknown. The aim of this study was thus to investigate the inputs of anthropogenic DOM from land-based aquaculture to the predominantly pristine river systems of North Patagonia. We hypothesized, that i) DOM exported from land-based aquaculture mainly consists of protein-like fluorescence (tyrosine and tryptophan) released from fish feces and food remains, and that ii) this DOM is highly degradable and therefore rapidly turned-over within the receiving streams. In the North Patagonian region we conducted a screening of ten land-based aquacultures and an intensive sampling campaign for one aquaculture. This was combined with longitudinal transects and a degradation experiment in order to couple the composition of DOM exported from land-based aquacultures to its degradability in streams. We measured dissolved organic carbon (DOC) concentration by high-temperature catalytic oxidation and DOM composition by fluorescence spectroscopy and parallel factor analysis. In the effluent of the ten screened aquacultures and in the repeated sampling of one aquaculture, we consistently found an increase of DOC concentrations and a dominance of protein-like fluorescence. The protein-like fluorescence rapidly disappeared downstream of the aquacultures, and in the degradation experiment. 21% of the DOC export from the repeatedly sampled aquaculture resulted from food addition and 76% from fish production. We conclude that large amounts of degradable DOM are exported from land-based aquacultures. This probably has strong effects on the ecological structure and function of North Patagonian streams, and similarly affected streams worldwide.

Colored dissolved organic matter dynamics and anthropogenic influences in a major transboundary river and its coastal wetland.

Most transboundary rivers and their wetlands are subject to considerable anthropogenic pressures associated with multiple and often conflicting uses. In the Eastern Mediterranean such systems are also particularly vulnerable to climate change, posing additional challenges for integrated water resources management. Comprehensive measurements of the optical signature of colored dissolved organic matter (CDOM) were combined with measurements of river discharges and water physicochemical and biogeochemical properties, to assess carbon dynamics, water quality, and anthropogenic influences in a major transboundary system of the Eastern Mediterranean, the Evros (or, Марица or, Meriç) river and its Ramsar protected coastal wetland. Measurements were performed over three years, in seasons characterized by different hydrologic conditions and along transects extending more than 70 km from the freshwater end‐member to two kilometers offshore in the Aegean Sea. Changes in precipitation, anthropogenic dissolved organic matter (DOM) inputs from the polluted Ergene tributary, and the irregular operation of a dam were key factors driving water quality, salinity regimes, and biogeochemical properties in the Evros delta and coastal waters. Marsh outwelling affected coastal carbon quality, but the influence of wetlands was often masked by anthropogenic DOM contributions. A distinctive five‐peak CDOM fluorescence signature was characteristic of upstream anthropogenic inputs and clearly tracked the influence of freshwater discharges on water quality. Monitoring of this CDOM fluorescence footprint could have direct applications to programs focusing on water quality and environmental assessment in this and other transboundary rivers where management of water resources remains largely ineffective.

Identifying the sources and fate of anthropogenically impacted dissolved organic matter (DOM) in urbanized rivers

Anthropogenic activities have dramatically changed the loads and compositions of dissolved organic matter (DOM) in urbanized streams. In this study, the spatial and temporal variations of DOM in the anthropogenically impacted Zhujiang River were investigated by analyzing the water samples in an upstream, urbanized area and downstream of the rivers on different days of one year. The results indicated that the levels of dissolved organic carbon (DOC) and total phosphorus (TP) were unaffected by seasonal changes, but the specific UV254 absorbance (SUVA) values and the total nitrogen (TN) content were greater in the winter than those in the summer. Parallel factor (PARAFAC) analysis of the excitation emission matrices (EEM) revealed the presence of three anthropogenically derived components [tryptophan-like (C1) and tyrosine-like proteins (C3) and anthropogenic humic substances (C5)] in the urbanized rivers, and they had greater seasonal and spatial variability than the terrestrial and microbial humic substances (C2 and C4). Cluster analysis revealed that treated wastewater was an important source of DOM in the urbanized streams. Photodegradation experiments indicated that the DOM in the populous area of the rivers had greater photodegradation potentials than that in the downstream region or in the natural waters. Interestingly, that the anthropogenic humic substances (C5) were considerably more photoreactive than the other four PARAFAC components, which exhibited a decrease of 80% after exposure to sunlight for 0.5 d. This study suggests that the treated wastewater could be an important input to the DOM in the urbanized rivers and the naturally occurring photodegradation could help in eliminating the anthropogenic DOM during their transport.

Dissolved oxygen and its response to eutrophication in a tropical black water river

The Siak is a typical, nutrient-poor, well-mixed, black water river in central Sumatra, Indonesia, which owes its brown color to dissolved organic matter (DOM) leached from surrounding, heavily disturbed peat soils. We measured dissolved organic carbon (DOC) and oxygen concentrations along the river, carried out a 36-h experiment in the province capital Pekanbaru and quantified organic matter and nutrient inputs from urban wastewater channels into the Siak. In order to consider the complex dynamic of oxygen in rivers, a box-diffusion model was used to interpret the measured data. The results suggest that the decomposition of soil derived DOM was the main factor influencing the oxygen concentration in the Siak which varied between approximately 100 and 140 micromol l(-1). Additional DOM input caused by wastewater discharges appeared to reduce the oxygen concentrations by approximately 20 micromol l(-1) during the peak-time in household water use in the early morning and in the early evening. Associated enhanced nutrient inputs appear to reduce the impact of the anthropogenic DOM by favoring the photosynthetic production of oxygen in the morning. A reduction of 20 micromol l(-1), which although perhaps not of great significance in Pekanbaru, has strong implications for wastewater management in the fast developing areas downstream Pekanbaru where oxygen concentrations rarely exceed 20 micromol l(-1).