Dissolved Organic Matter Abundance Research Articles

Coupling of anthropogenic activities and natural factors on dissolved organic matter: Insights from coastal urban rivers in southern China

Accelerated urbanization has reshaped the biogeochemistry of dissolved organic matter (DOM) in urban rivers, yet the interplay between anthropogenic and natural influences on riverine DOM remains unclear. This study utilized absorbance and fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC), to explore the spatiotemporal distribution of DOM in twenty coastal rivers located in a highly urbanized area. Findings highlight increased DOM abundance, especially the protein-like component (C2: 1.48 RU in urban areas and 0.24 RU in suburban areas), in the rivers of urban areas, contrasted by seasonal shifts of chromophoric DOM (CDOM) and humic-like DOM in the rivers of suburban areas (a350: 3.18 m−1 in the wet season and 1.23 m−1 in the dry season). Tidal mixing’s role in DOM distribution is evidenced by diurnal salinity changes and its inverse relationship with DOM abundance. Notably, the Shenzhen River’s unique DOM composition (a higher abundance of humic-like DOM and a lower abundance of protein-like DOM) suggests agricultural impacts. Strong correlations (R2 values reaching up to 0.87) between spectral DOM indicators and chemical oxygen demand (COD) underscore the great potential of spectral methods for water quality monitoring. Overall, this study illuminates the coupled effects of urbanization and natural factors on riverine DOM, offering insights for the biogeochemical cycling of DOM and water quality management in urban rivers, with implications for similar urbanized regions globally.

Characterization of natural and anthropogenic dissolved organic matter in the yangtze river basin using FT-ICR MS

Dissolved organic matter (DOM) is a complex mixture that plays a crucial role in global carbon cycling and climate dynamics. Understanding the chemical composition of DOM is crucial for studying its biogeochemical behavior. However, identifying individual DOM molecules is challenging. Here, using ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry and an in-house database, we developed a framework to investigate DOM characteristics in natural water. Through the developed approach, we successfully identified thousands of individual DOM molecules in the water bodies of the Yangtze River Basin. For the first time, the proportions of natural and anthropogenic organics within DOM were revealed. In total, 9006 unambiguous molecular formulas were assigned to DOM in the Yangtze River Basin. The proportions of CHNO and CHOS compounds increased from upstream to downstream regions. Moreover, 1099 DOM compounds were tentatively identified, with 85 % being endogenous organics and 15 % being exogenous organics. Notably, lipids and pharmaceuticals and personal care products were the most frequently detected endogenous and exogenous compounds. The spatial variation of the identified DOM indicated anthropogenic discharges considerably increased both the number and abundance of DOM in the downstream Yangtze River Basin. This study highlighted the importance of anthropogenic impacts on DOM in water.

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.

Response mechanism of soil leachate and disinfection by-product formation to extreme precipitation events under continuous drought scenario

In this study, a rainfall simulation device was employed to investigate the response mechanism of soil leachate and disinfection by-products formation potential (DBPsFP) to extreme precipitation events. The results revealed that the aromaticity of dissolved organic matter (DOM) and the concentration of hydrophobic DOM containing aromatic carbon groups in leachate decreased with rising temperature. The humification degree of DOM decreased at 25 °C (99 mm/h), while the humification degree and protein-like level of DOM increased under high temperatures droughts (45 °C and 65 °C). Higher temperatures resulted in the leach of more microbial-derived humus and low molecular phenolic compounds from soil and broadened the range of molecular weight distribution. Increasing temperature increased DBPsFP and DBPs species and caused the precursors of haloacetic acids (HAAs) in leachate to become more hydrophobic, while the precursors of trihalomethanes (THMs) became more hydrophilic. Most importantly, the increased temperature attenuated the rainfall-mediated dilution of organic pollutant concentration, and temperature has a more significant effect than extreme rainfall in DOM abundance and the formation potential (or species) of DBPs. The results help to better understand the impact of climate change on the physicochemical processes of water quality.

Coagulation pretreatment coupled with indigenous microalgal-bacterial consortium system for on-site treatment of rural black wastewater

Improper treatment of rural black wastewater (RBW) presents substantial challenges, including the wastage of resource, environmental contamination, and economic consequences. This study proposed an integrated process for RBW treatment, consisting of coagulation/flocculation (C/F) pretreatment and subsequent inoculation of indigenous microalgal-bacterial consortium (IMBC) for nitrogen recovery, namely C/F-IMBC process. Specifically, the optimal C/F conditions (polyaluminium chloride of 4 g/l, polyacrylamide of 50 mg/l, and pH of 6) were determined through a series of single-factor experiments, considering CN, turbidity, and dissolved organic matter (DOM) removal, economic cost, and potential influence on the water environment. Compared to the sole IMBC system for RBW treatment, the proposed C/F-IMBC process exhibited a remarkable 1.23-fold increase in microalgal growth and a substantial 17.6–22.6 % boost in nitrogen recovery. The altered RBW characteristic induced by C/F pretreatment was supposed to be responsible for the improved system performance. In particular, the abundance of DOM was decreased and its composition was simplified after C/F pretreatment, based on the analysis for excitation-emission matrices with parallel factor and gas chromatography–mass spectrometry, thus eliminating the potential impacts of toxic DOM components (e.g., Bis(2-ethylhexyl) phthalate) on IMBC activity. It should also be noted that C/F pretreatment modified microbial community structure as well, thereby regulating the expression of nitrogen-related genes and enhancing the system nitrogen recovery capacity. For instance, the functional Cyanobacteria responsible for nutrient recovery was enriched by 1.95-fold and genes involved in the assimilatory nitrate reduction to ammonia pathway were increased by 1.52-fold. These fundamental findings are expected to offer insights into the improvement of DOM removal and nitrogen recovery for IMBC-based wastewater treatment system, and provide valuable guidance for the development of sustainable on-site RBW treatment technologies.

Identification of methane cycling pathways in Quaternary alluvial-lacustrine aquifers using multiple isotope and microbial indicators

Groundwater rich in dissolved methane is often overlooked in the global or regional carbon cycle. Considering the knowledge gap in understanding the biogeochemical behavior of methane in shallow aquifers, particularly those in humid alluvial-lacustrine plains with high organic carbon content, we investigated methane sources and cycling pathways in groundwater systems at the central Yangtze River basins. Composition of multiple stable isotopes (2H/18O in water, 13C in dissolved inorganic carbon, 13C/2H in methane, and 13C in carbon dioxide) was combined with the characteristics of microbes and dissolved organic matter (DOM) in the study. The results revealed significant concentrations of biogenic methane reaching up to 13.05 mg/L in anaerobic groundwater environments with abundant organic matter. Different pathways for methane cycling (methanogenic CO2-reduction and acetate-fermentation, and methane oxidation) were identified. CO2-reduction dominated acetate-fermentation in the two methanogenic pathways primarily associated with humic DOM, while methane oxidation was more closely associated with microbially derived DOM. The abundance of obligate CO2-reduction microorganisms (Methanobacterium and Methanoregula) was higher in samples with substantial CO2-reduction, as indicated by isotopic composition. The obligate acetate-fermentation microorganism (Methanosaeta) was more abundant in samples exhibiting evident acetate-fermentation. Additionally, a high abundance of Candidatus Methanoperedens was identified in samples with apparent methane oxidation. Comparing our findings with those in other areas, we found that various factors, such as groundwater temperature, DOM abundance and types, and hydrogeological conditions, may lead to differences in groundwater methane cycling. This study offered a new perspective and understanding of methane cycling in worldwide shallow alluvial-lacustrine aquifer systems without geothermal disturbance.

Direct and Indirect Effects of Land Use on Dissolved Organic Matter in a Typical Karst River

Land use can directly affect the abundance of riverine dissolved organic matter (DOM) by transporting terrestrial organic matter to rivers and can also indirectly enhance local production of DOM by increasing riverine nutrient loading. This study investigated the characteristics and spatial distribution of DOM components in the Furong River during the rainy season (July) using ultraviolet-visible light absorption spectroscopy (UV-VIS) and three-dimensional excitation emission matrix fluorescence spectroscopy-parallel factor analysis (EEM-PARAFAC) techniques. Furthermore, correlation analysis and the partial least squares path model (PLS-PM) were used to identify and quantify the direct and indirect impacts of land use on DOM at multiple scales. The results revealed that:① the direct effects of land use on DOM were generally stronger than the indirect effects. ② The responses of different DOM components to riverine nutrient status and land use varied, with dissolved organic carbon (DOC) and colored dissolved organic matter (CDOM) components being more susceptible to riverine nutrient status and fluorescent dissolved organic matter (FDOM) being more sensitive to land use. ③ The direct impact intensity of land use on DOC and CDOM fluctuated slightly with the spatial scale, but the total impact intensity had no visible spatial scale difference, and the direct impact intensity on the FDOM component decreased with the increase in spatial scale. ④ Dryland, urban and other construction land, patch density (PD), edge density (ED), and Shannon's diversity index (SHDI) were typical land use metrics that exacerbated DOM abundance, whereas paddy field, shrubland, largest patch index (LPI), and aggregation index (AI) were typical land use metrics that effectively mitigated DOM abundance. Total nitrogen (TN), nitrate nitrogen (NO3--N), and dissolved total phosphorus (DTP) were water quality parameters that were significantly affected by land use and were closely related to DOM components, that is, nitrogen and phosphorus played an important "intermediary" role in "land use-riverine DOM." FDOM could be used as indicators to measure the strength of terrestrial organic matter directly input to rivers by land use.

Rainwater extracting characteristics and its potential impact on DBPs generation: A case study

Frequent extreme precipitation events due to global warming can lead to large amounts of pollutants entering source water bodies via surface runoff and wet deposition, thus posing a threat to water supply security. In order to better understand the source characteristics and leaching mechanisms of rainwater dissolved organic matter (DOM), as well as its disinfection by-products formation potential (DBPsFP) during disinfection processes, rainwater samples were collected and extracting experiments were conducted. Three components were identified in rainwater through Parallel factor (PARAFAC) analysis, which were microbial humic-like component C1 (63.1 %), protein (tryptophan-like) component C2 (28.9 %), marine or terrestrial humic-like component C3 (8.1 %). The average molecular weight of rainwater fractions was ordered: hydrophobic neutral (HON) < hydrophobic bases (HOB) < hydrophobic acidic (HOA) < hydrophilic (HIS). The HOA and HON fractions of rainwater were the dominant precursors of trihalomethanes (THMs), while the rainwater HON fraction and hydrophilic fraction were the main precursor of haloacetic acids (HAAs) and trihloroacetonitrile (TCAN), respectively. Subsoil extracts had a higher concentration of dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) than topsoil extracts. Partial least squares path modeling (PLS-PM) demonstrated that the extraction temperature was the dominant factor affecting the abundance of DOM in the topsoil extracts (R2 = 0.28), while the extraction time accounted more for the abundance of fluorescence substance and physicochemical indices in the subsoil extracts (R2 = 0.23 and 0.32, respectively). These results provide key information for controlling the impacts of global warming, in particular the risk of water sources being heavily contaminated by request rainfalls.

Comparisons in molecular weight distributions and size-dependent optical properties among model and reference natural dissolved organic matter.

Humic acid (HA) and reference natural organic matter (NOM) have been widely used in environmental assessment, biogeochemistry, and ecotoxicity studies. Nevertheless, similarities and differences among the commonly used model/reference NOMs and bulk dissolved organic matter (DOM) have rarely been systematically evaluated. In this study, HA, SNOM (Suwannee River NOM) and MNOM (Mississippi River NOM), both from International Humic Substances Society, and freshly collected unfractionated NOM (FNOM) were concurrently characterized to evaluate their heterogeneous nature and size-dependent chemical properties. We found that molecular weight distributions, PARAFAC-derived fluorescent components, and size-dependent optical properties are NOM-specific and highly variable with pH. The < 1kDa DOM abundance followed the order of HA < SNOM < MNOM < FNOM. In addition, FNOM was more hydrophilic and contained more protein-like and autochthonous components with a higher UV-absorbance ratio index (URI) and biological fluorescenceindex, whereas HA and SNOM contained more allochthonous, humic-like components with a higher aromaticity and lower URI. Significant differences in molecular composition and size spectra between FNOM and model/reference NOMs suggest that environmental role of NOMs should be evaluated at the levels of molecular weight and functionalities under the same experimental conditions and that HA and SNOM may not represent bulkNOM in the environment. This study provides new information about similarities and differences in DOM size-spectra and chemical properties between reference NOMs and in-situ NOM and highlights the need to better understand the heterogenous roles of NOMs in regulating the toxicity/bioavailability and environmental fate of pollutants in aquatic environments.

Spatiotemporal response of dissolved organic matter diversity to natural and anthropogenic forces along the whole mainstream of the Yangtze River

The Yangtze River, the largest river in Asia, plays a crucial role in linking continental and oceanic ecosystems. However, the impact of natural and anthropogenic disturbances on composition and transformation of dissolved organic matter (DOM) during long-distance transport and seasonal cycle is not fully understood. By using a combination of elemental, isotopic and optical techniques, as well as Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), we investigated DOM abundance and composition along the whole mainstream at highly spatial resolution in the dry and early wet seasons. Our findings showed that the concentration and flux of dissolved organic carbon (DOC) in the Yangtze River was much lower compared with other worldwide larger rivers. The distribution of δ13CDOC and higher abundance of humic-like fluorescent component and highly unsaturated and phenolics (HUPs) compound reflected a prominent contribution of allochthonous DOM. Further optical and molecular analysis revealed humic-like fluorescent components were coupled with CHO molecules and HUPs compound with higher aromatic, unsaturated, molecular weight and stable characteristics between upstream and midstream reaches. With increasing agricultural and urban land downstream, there were more heteroatomic formulae and labile aliphatic and protein-like compounds which were derived from human activities and in situ primary production. Meanwhile, DOM gradually accumulates with slow water flow and additional autochthonous organics. Weaker solar radiation and water dilution during the dry/cold season favours highly aromatic, unsaturated and oxygenated DOM compositions. Conversely, higher discharge during the wet/warm season diluted the terrestrial DOM, but warm temperatures could promote phytoplankton growth that releases labile aliphatic and protein-like DOM. Besides, chemical sulfurization, hydrogenation and oxygenation were found during molecular cycling processes. Our research emphasizes the active response of riverine DOM to natural and anthropogenic controls, and provides a valuable preliminary background to better understand the biogeochemical cycling of DOM in a larger river.

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’.

Transformation of dissolved organic matter during UV/peracetic acid treatment

Peracetic acid combined ultraviolet (UV/PAA) process has garnered growing attention as a promising advanced oxidation process (AOP) for wastewater treatment, but the corresponding transformation of ubiquitous dissolved organic matter (DOM) under this AOP remains unknown. This study systematically investigated the changes in characteristics and composition of DOM under UV/PAA, as well as the underlying mechanisms by multiple spectroscopic analyses and Fourier transform ion cyclotron resonance mass spectrometry. UV/PAA treatment dramatically decreased aromaticity, apparent molecular weight, and fluorescent abundance of DOM with the production of more oxidized and saturated compounds. The reactive species (i.e., ·OH and CH3C(O)O·/CH3C(O)OO·) in UV/PAA contributed primarily to DOM changes but showed different reaction selectivity and mechanisms. ·OH reacts with DOM components and mainly yields oxygenation products via a radical addition pathway. Comparatively, the electron transfer route is more likely to occur in CH3C(O)O·/CH3C(O)OO·-induced DOM transformation. Aside from oxygenation products, electron transfer could exclusively generate decarboxylation products and distinguishes CH3C(O)O·/CH3C(O)OO·-based AOPs from ·OH-based AOPs. These findings significantly improve knowledge of DOM alterations under UV/PAA AOP at both the bulk and molecular levels.

Improvement criteria for different advanced technologies towards bio-stabilized leachate based on molecular subcategories of DOM

Considering dissolved organic matter (DOM) molecules, the present study is an attempt to unravel the individual removal targets of nine advanced treatment technologies for bio-stabilized landfill leachate. For the eight DOM molecular subcategories, preferable technologies and removal rates were as follows: lipids ‒ powdered activated carbon (PAC) adsorption (97%) and Fenton (97%); proteins ‒ extended electrolysis (92%) and Fenton (92%); and lignins/carboxylic rich alicyclic molecules (CRAM)-like organics ‒ Fenton (90%) and extended electrolysis (75%). As to individual technologies, Fenton, PAC adsorption, extended electrolysis, and reverse osmosis (RO) had the highest removal rates based on the intensity and abundance of DOM. As to the improved technology combinations, “Fenton with PAC adsorption” and “PAC adsorption with reverse osmosis” were then recommended according to the target complementarity in compound intensity and abundance. The study suggested that the treatment strategy of an unknown recalcitrantly biodegraded wastewater could be designed in a tailored way based on the subcategorized DOM characteristics of the refractory wastewater.

Molecular weight fractionated characterization of dissolved organic matter and its correlation with water quality in the Bahe River Basin, Northwest China

Dissolved organic matter (DOM) is one of the core carriers of organic matter decomposition and nutrient regeneration in water. It is an important link of biogeochemical cycle of carbon and nitrogen, and the key content of water environmental science research. We used liquid chromatography-organic carbon detection-organic nitrogen detection (LC-OCD-OND) to investigate the molecular weight distribution of riverine DOM in the Bahe River of Xi'an City and further analyzed its correlation with water quality. The results showed that riverine DOM was composed of biopolymers, humic substances, humus degradation products, and low molecular-weight neutrals, with the ave-rage concentration of 0.15, 1.75, 0.48, 0.36 and 0.002 mg·L-1, respectively. The DOM along the river was in order of urban＞ town＞ river source. The humic substances with molecular weight of 1000-20000 Da accounted for 49.0% of total DOM which followed the order of town＞ waste water treatment plants (WWTPs) effluents＞river estuary＞ river source. The biopolymers with the molecular weight of >20000Da accounted for 5.1% of total DOM, with the sequence of WWTPs effluents＞river estuary＞river source＞town. The allochthonous (terrigenous) DOM produced by WWTPs effluents had the greatest contribution to the riverine DOM. The fractions of DOM with different molecular weights had significant correlations with water quality parameters. The results showed that the molecular weight fractions and abundance of DOM based on LC-OCD-OND could be used as a comprehensive index for water quality monitoring, to characterize the spatial heterogeneity of river water quality, and used for quantitative identification and source apportionment of pollutant components.

Molecular size-dependent abundance and composition of dissolved organic matter in river, lake and sea waters

Dissolved organic matter (DOM) is ubiquitous in natural waters. The ecological role and environmental fate of DOM are highly related to the chemical composition and size distribution. To evaluate size-dependent DOM quantity and quality, water samples were collected from river, lake, and coastal marine environments and size fractionated through a series of micro- and ultra-filtrations with different membranes having different pore-sizes/cutoffs, including 0.7, 0.4, and 0.2 μm and 100, 10, 3, and 1 kDa. Abundance of dissolved organic carbon, total carbohydrates, chromophoric and fluorescent components in the filtrates decreased consistently with decreasing filter/membrane cutoffs, but with a rapid decline when the filter cutoff reached 3 kDa, showing an evident size-dependent DOM abundance and composition. About 70% of carbohydrates and 90% of humic- and protein-like components were measured in the <3 kDa fraction in freshwater samples, but these percentages were higher in the seawater sample. Spectroscopic properties of DOM, such as specific ultraviolet absorbance, spectral slope, and biological and humification indices also varied significantly with membrane cutoffs. In addition, different ultrafiltration membranes with the same manufacture-rated cutoff also gave rise to different DOM retention efficiencies and thus different colloidal abundances and size spectra. Thus, the size-dependent DOM properties were related to both sample types and membranes used. Our results here provide not only baseline data for filter pore-size selection when exploring DOM ecological and environmental roles, but also new insights into better understanding the physical definition of DOM and its size continuum in quantity and quality in aquatic environments.

Spatiotemporal variations in the abundance and composition of bulk and chromophoric dissolved organic matter in seasonally hypoxia-influenced Green Bay, Lake Michigan, USA

Green Bay, Lake Michigan, USA, is the largest freshwater estuary in the Laurentian Great Lakes and receives disproportional terrestrial inputs as a result of a high watershed to bay surface area ratio. While seasonal hypoxia and the formation of “dead zones” in Green Bay have received increasing attention, there are no systematic studies on the dynamics of dissolved organic matter (DOM) and its linkage to the development of hypoxia. During summer 2014, bulk dissolved organic carbon (DOC) analysis, UV–vis spectroscopy, and fluorescence excitation-emission matrices (EEMs) coupled with PARAFAC analysis were used to quantify the abundance, composition and source of DOM and their spatiotemporal variations in Green Bay, Lake Michigan. Concentrations of DOC ranged from 202 to 571μM-C (average=361±73μM-C) in June and from 279 to 610μM-C (average=349±64μM-C) in August. In both months, absorption coefficient at 254nm (a254) was strongly correlated to bulk DOC and was most abundant in the Fox River, attesting a dominant terrestrial input. Non-chromophoric DOC comprised, on average, ~32% of bulk DOC in June with higher terrestrial DOM and ~47% in August with higher aquagenic DOM, indicating that autochthonous and more degraded DOM is of lower optical activity. PARAFAC modeling on EEM data resulted in four major fluorescent DOM components, including two terrestrial humic-like, one aquagenic humic-like, and one protein-like component. Variations in the abundance of DOM components further supported changes in DOM sources. Mixing behavior of DOM components also indicated that while bulk DOM behaved quasi-conservatively, significant compositional changes occurred during transport from the Fox River to the open bay.

Dynamics of dissolved organic carbon and total dissolved nitrogen in Maryland's coastal bays

Dissolved organic matter (DOM) provides nutrients and energy subsidies for harmful algal blooms in Maryland's Coastal Bays (MCBs, USA). The composition, sources and dynamics of DOM in MCBs are not well known. In this study, dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) were monitored monthly over a period of one year (July 2011 to June 2012) at 13 stations in the MCBs. Absorption and fluorescence spectroscopy were used to characterize DOM composition and track terrestrial inputs versus aquatic sources of DOM. Results show that DOC and TDN concentrations in the MCBs (187–501 μM and 19.4–40.6 μM) were comparable to eutrophic coastal waters in the United States but much higher than the mid-Atlantic Bight. This suggests that the MCBs are a DOM source for the coastal ocean. Spatially, nearshore sites had relatively higher DOC and TDN concentrations and terrestrially-derived aromatic DOM (indicated by high humification index) than the bays that were directly connected to the Atlantic Ocean. Seasonally, DOC from the main body of the MCBs (Chincoteague and Assawoman Bays) displayed a pronounced seasonal pattern with the highest values occurring in summer. Protein-like DOM from algal/bacterial inputs (indicated by high biological freshness index or fluorescence index) was also highest in summer but then decreased gradually until April. DOC concentrations at the nearshore site were highest in later spring, probably due to terrestrial inputs. Conversely, TDN concentrations in smaller bays with faster flushing rates (Newport, Sinepuxent and Isle of Wight Bays) were highest in April, probably due to watershed nitrogen inputs. This spring TDN peak was not apparent in the main body of the MCBs, which have longer flushing times (indicating stronger biological nitrogen uptake). This study suggests that DOM in eutrophic, shallow coastal bays such as the MCBs consists of a large fraction of protein-like components from local algal/microbial sources during summer. This enhanced primary productivity is likely fueled by watershed nitrogen inputs from agricultural and urban land use during spring. Further insights regarding spatiotemporal variations and controls of DOM abundance, composition and sources in the MCBs can be helpful in guiding and prioritizing coastal restoration efforts for reducing eutrophication and water quality degradation.

Occurrence, polarity and bioavailability of dissolved organic matter in the Huangpu River, China

Dissolved organic matter (DOM) plays an important role in biogeochemical cycles in aquatic ecosystem. To investigate the characteristics of DOM in Huangpu River (the last tributary of the Yangtze River), surface water samples were collected along the river from December 2011 to June, 2013. The concentrations of dissolved organic carbon (DOC), the absorbance and fluorescence spectrum of DOM in water samples were measured. Fluorescent DOM in the Huangpu River was decomposed into four components by the parallel factor analysis (PARAFAC), including one humic-like substance and three protein-like substances. It showed that high spatial variability of DOC concentration was observed in the upstream water compared to the downstream water, and so did the absorbance coefficients of chromophoric dissolved organic matter and the total fluorescence intensities of different PARAFAC components of DOM. Furthermore, there was a large difference between the polarity and bioavailability of DOM in the Huangpu River. Polar compounds dominated tyrosine-like component of fluorescent DOM in all seasons. Tryptophan-like and humic-like substances had more polar fraction in summer and autumn than those in winter, while aromatic protein-like materials had the highest polar fraction in winter. Almost all of fluorescent DOM components were refractory in spring, while less than 20% of fluorescent DOM in average were biodegradable within 4weeks in other seasons. We concluded that the spatial variation in the abundance of DOM in the Huangpu River is mainly affected by the water discharges from the Hangjiahu Plain and the seasonal difference in polarity and bioavailability of DOM is largely determined by its origins.

Hydroxyl radical ([rad]OH) scavenging in young and mature landfill leachates

The final discharge point for collected landfill leachates is frequently the local municipal wastewater treatment facility. The salinity, color, nutrient, and anthropogenic organics contamination of leachates often necessitate some form of pre-treatment. When advanced oxidation processes (AOPs) are considered for pre-treatment, the unique composition of dissolved organic matter (DOM) and the relatively high concentrations of some inorganic solutes in leachate will inhibit treatment efficiency. The most important benchmark for design of AOPs is the expected steady-state production of free radical (OH). Without a quantitative assessment of total OH consumption in high-strength waste water, like a landfill leachate, efficient AOP treatment is uncertain. For this reason, two landfill leachates, distinct in color, DOM, and age of landfill, were characterized for OH-scavenging using an established competition kinetics method. After stripping the samples of inorganic carbon, the DOM in leachate from mature (stabilized) landfill was found to react with OH at a rate of 9.76 × 108 M−1s−1. However, DOM in leachate from newer landfill was observed to scavenge available OH at a faster rate (8.28 × 109 M−1s−1). The combination of fast rate of reaction with OH and abundance of DOM in the sampled leachate severely limited the contribution of OH to degradation of an O3- and OH-labile organic probe compound (bisphenol-a) in oxidized mature leachate (fOH = 0.03). Substantial dosing of both O3 and H2O2 (>70 mg/L and >24 mg/L, respectively) may be required to see at least 1-log-removal (>90%) of an OH-selective leachate contaminant (i.e., parachlorobenzoic acid) in a mature landfill leachate.

Revealing Sources and Distribution Changes of Dissolved Organic Matter (DOM) in Pore Water of Sediment from the Yangtze Estuary

Dissolved organic matter (DOM) in sediment pore waters from Yangtze estuary of China based on abundance, UV absorbance, molecular weight distribution and fluorescence were investigated using a combination of various parameters of DOM as well as 3D fluorescence excitation emission matrix spectra (F-EEMS) with the parallel factor and principal component analysis (PARAFAC-PCA). The results indicated that DOM in pore water of Yangtze estuary was very variable which mainly composed of low aromaticity and molecular weight materials. Three humic-like substances (C1, C2, C4) and one protein-like substance (C3) were identified by PARAFAC model. C1, C2 and C4 exhibited same trends and were very similar. The separation of samples on both axes of the PCA showed the difference in DOM properties. C1, C2 and C4 concurrently showed higher positive factor 1 loadings, while C3 showed highly positive factor 2 loadings. The PCA analysis showed a combination contribution of microbial DOM signal and terrestrial DOM signal in the Yangtze estuary. Higher and more variable DOM abundance, aromaticity and molecular weight of surface sediment pore water DOM can be found in the southern nearshore than the other regions primarily due to the influence of frequent and intensive human activities and tributaries inflow in this area. The DOM abundance, aromaticity, molecular weight and fluorescence intensity in core of different depth were relative constant and increased gradually with depth. DOM in core was mainly composed of humic-like material, which was due to higher release of the sedimentary organic material into the porewater during early diagenesis.