Properties Of Dissolved Organic Matter Research Articles

Source tracking of dissolved organic nitrogen at the molecular level during storm events in an agricultural watershed

Accelerated export of nitrogen-containing dissolved organic matter (DOM) or dissolved organic nitrogen (DON) to streams and rivers from agricultural watersheds has been reported worldwide. However, few studies have examined the dynamics of DOM molecular composition with the attention paid to the relative contributions of DON from various sources altered with flow conditions. In this study, end-member mixing analysis (EMMA) was conducted with the optical properties of DOM to quantify the relative contributions of several major organic matter sources (litter, reed, field soil, and manure) in two rivers of a small agricultural watershed. DOC and DON concentration increased during the storm events with an input of allochthonous DOM as indicated by an increase in specific ultraviolet absorbance at 254 nm (SUVA254) and a decrease in biological index (BIX), fluorescence index (FI), and protein-like component (%C3) at high discharge. EMMA results based on a Bayesian mixing model using stable isotope analysis in R (SIAR) were more accurate in source tracking than those using the traditional IsoSource program. Manure (>30%) and field soil (also termed as “manure-impacted field soil”) (>23%) end-members revealed their predominant contributions to the riverine DOM in SIAR model, which was enhanced during the storm event (up to 56% and 38%, respectively). The molecular composition of the riverine DOM exhibited a distinct footprint from the manure and manure-impacted field soil, with a larger number of CHON formulas and abundant polyphenols and condensed aromatics in peak flow samples in the studied rivers. The riverine DOM during peak flow contained many unique molecular formulas in both rivers (4980 and 2082) of which >60% originated from manure and manure-impacted field soil. Combining the EMMA with DOM molecular composition clearly demonstrated the effect of manure fertilizer on the riverine DOM of the watershed with intensive agriculture. This study provides insights into the source tracking and regulation of DON leaching from anthropogenically altered river systems worldwide.

Coprecipitation of humic acid and phosphate with Fe(III) enhances the sequestration of carbon and phosphorus in sediments

The coprecipitation of dissolved organic matter (DOM) and phosphate with Fe(III) at the sediment-water interface plays an important role in the biogeochemical cycle of organic carbon (OC) and phosphorus (P) in aquatic ecosystems. However, studies remain limited towards understanding the strength of ternary DOM-phosphate-Fe(III) coprecipitation in sequestering OC and P. Here, we investigated the behaviors of humic acid (HA) and phosphate during their coprecipitation with Fe(III) and compared the coprecipitation behaviors with those during the adsorption process. The results showed that the coprecipitation of HA and phosphate with Fe(III) enhanced as pH decreased or initial Fe(III) concentrations increased. The presence of phosphate had a moderate inhibition effect on HA coprecipitation, leading to 3%–37% of reduction in precipitated HA. Changes in optical properties of DOM (i.e., SUVA254, E2/E3, and fluorescent components) showed that macromolecular, aromatic molecules preferentially coprecipitated, and this selectivity pattern was not influenced by the presence of phosphate. Compared to the adsorption of HA and phosphate to goethite, coprecipitation with Fe(III) displayed stronger binding ability, sequestering more than10 times of HA and phosphate, and was more efficient in sequestering protein-like compounds. The inhibitory effect of phosphate on HA sequestration was weaker during coprecipitation than during adsorption. Moreover, coprecipitation led to a lower degree of compositional fractionation of HA than adsorption, which may be explained by that inclusion, an important pathway for coprecipitation, has low selectivity for chemical compositions. Collectively, our results demonstrate that coprecipitation plays a crucial role in sequestering both OC and P in aquatic systems, arguing that the formation of ternary OC-Fe-P coprecipitates may be an important pathway for sequestering OC and P over a long term and reducing the internal loading of P in eutrophic lakes.

Photochemistry of dissolved organic matter in water from the Pearl river (China): Seasonal patterns and predictive modelling

Photochemical properties of dissolved organic matter (DOM) vary widely in natural and engineered water systems due to the different dominant compositions. However, seasonal patterns of DOM photochemical properties in urban rivers remain unclear. In this study, two seasons (wet and dry) of water samples were collected from eleven sites throughout the Pearl River (China) to investigate the spatiotemporal variability of DOM optical and photochemical properties. The optical properties of DOM in the Pearl River were characterized by UV–vis and fluorescence spectroscopies, which showed the substantial decrease in absorption coefficient and fluorescence intensity and increase in absorbence ratio (E2/E3) and specific absorption coefficient (SUVA) from the wet to dry season. The photochemical properties in terms of the apparent quantum yields of 3DOM*, 1O2 and ·OH from DOM (Φ3DOM*, Φ1O2 and Φ·OH, DOM) under illumination also displayed a significant decrease from the wet to the dry season. Spearman's rank correlation analysis revealed the strongest relationships between Φ3DOM*, Φ1O2 and Φ·OH, DOM and the relative abundance of microbial humic-like component (C2%) derived from parallel factor analysis (PARAFAC). Partial least squares regression (PLSR) modelling exhibited an excellent prediction strength for steady-state concentrations of 1O2 ([1O2]ss) and ·OH ([·OH]ss) with adjusted R2 values of 0.85 and 0.91, respectively, by using DOC concentration ([DOC]), optical properties, nitrate and nitrite concentrations as the response variables. In addition, the model identified that the Fmax of humic-like component C4 (Fmax-C4) was the most effective predictor amongst the used response variables. This study provides an approach to describe and predict the seasonal patterns of DOM photochemical properties in urbanized rivers, offering a good understanding of the formation mechanism of reactive species from river DOM.

Insight into variations of DOM fractions in different latitudinal rural black-odor waterbodies of eastern China using fluorescence spectroscopy coupled with structure equation model

The structural compositions of dissolved organic matter (DOM) could profoundly affect formation and evolution of black-odor waterbodies (BOWs). In this study, 81 samples of BOWs were collected from three different latitudinal rural regions in eastern China, including low, middle and high latitude regions. Based on fluorescence index (FI) and biological index (BIX) deduced from excitation-emission matrices (EEMs) of rural BOWs, biological source of DOM was dominant in low latitude, while DOM derived from both biological and terrestrial in mid-latitude and high-latitude. Furthermore, humification degree of DOM in the former was lower than those in the latter based on humification index (HIX) deduced from EEMs. Seven fluorescence components of DOM were extracted by EEMs combined with parallel factor analysis: components 1 and 2 (C1 and C2) known as tryptophan-like substances, C3 and C4 associated with tyrosine-like, C5 related with biological byproducts, C6 relative to fulvic-like, and C7 referred as humic-like. The roughly decreasing order of percentages in DOM fractions from the rural BOWs was tyrosine-like > tryptophan-like > fulvic-like > microbial byproduct > humic-like in three regions. According to hierarchical cluster analysis and redundancy analysis, the autochthonous fresh DOM was dominant in low latitudinal rural BOWs, which was relative to actions of phytoplankton and microorganisms. However, humification degree of DOM increased with a rise in latitude, which could attribute to variations of climate and agriculture industrial structure. Based on structure equation model, the C5 and FI were the potential factors of the rural BOWs, which suggested that microbial activity and pollution sources should affect formation and evolution of rural BOWs. These findings are conductive to reveal composition and fluorescence properties of DOM and in recognizing the potential factors of forming mechanism in rural BOWs, which could provide basic theoretical support for policymakers to regulate and treat it.

Application of UV absorbance and electron-donating capacity as surrogates for micropollutant abatement during full-scale ozonation of secondary-treated wastewater

Ozonation of secondary-treated wastewater for the abatement of micropollutants requires a reliable control of ozone doses. Changes in the UV absorbance of dissolved organic matter (DOM) during ozonation allow to estimate micropollutant abatement on-line and were therefore identified as feed-back control parameter. In this study, the suitability of the electron-donating capacity (EDC) as an additional surrogate parameter which is independent of optical DOM properties was evaluated during full-scale ozonation. For this purpose, a recently developed EDC analyzer was enhanced to enable continuous on-line EDC and UV absorbance measurements. During a multi-week monitoring campaign at the wastewater treatment plant of Zurich, Switzerland, specific ozone doses were varied from 0.13 to 0.91 mgO3⋅mgDOC−1 and selected micropollutants with different ozone reactivities were analyzed by LC-MS in conjunction with bromate analysis by IC-MS. In agreement with previous laboratory studies, the relative residual UV absorbance and EDC both decreased exponentially as a function of the specific ozone dose and, in comparison to the residual UV absorbance, residual EDC values showed a more pronounced decrease at low specific ozone doses ≤0.34 mgO3⋅mgDOC−1. Logistic regression models allowed to estimate relative residual micropollutant concentrations in the ozonation effluent using either the residual UV absorbance or EDC as explanatory variable. Averaging those models along the explanatory variables allowed to estimate target values in relative residual UV absorbances and EDC for specific micropollutant abatement targets. In addition, both parameters allowed to identify conditions with elevated conversions of bromide to bromate. Taken together, these findings show that the integration of relative residual EDC values as a second control parameter can improve existing absorbance-based ozonation control systems to meet micropollutant abatement targets, particularly for treatment systems where low ozone doses are applied.

Modeling and elucidation the effects of iron deposits on chlorine decay and trihalomethane formation in drinking water distribution system

Iron deposits stimulate chlorine consumption and trihalomethane (THM) formation in drinking water distribution systems through distinct mechanisms. In this study, a second-order chlorine decay model with a variable reaction-rate coefficient was developed to quantitatively evaluate the influences of iron deposits on chlorine reactions by considering the characteristics of dissolved organic matter (DOM), the type and dosages of deposits, as well as the initial chlorine concentrations. Based on a reliable prediction of residual chlorine, the concept that THM formation had a linear relationship with chlorine consumption was further validated by chlorination of DOM in the presence of iron deposits. Due to the catalysis influences, the reactivity of DOM towards chlorine decay or THM formation was accelerated. Although iron deposits activated the reactivity of DOM with bromine and chlorine, THM slightly shifted toward chlorinated species. Due to the adsorption influences, the maximum chlorine demand increased with the increasing deposit dosages whereas the extent of enhancement mainly relied on the DOM properties. Low-molecular-weight DOM with a hydrophilic characteristic was prone to be elevated by iron deposits. Based on the model simulation, approximately 20% of chlorine consumption and 37% of THM formation were contributed by deposits after 168 h reaction. The data provided herein emphasize the role of iron deposits in chlorine consumption and THM formation, which assist the water quality management in drinking water distribution systems.

Binding strength of mercury (II) to different dissolved organic matter: The roles of DOM properties and sources

Dissolved organic matter (DOM) influences the environmental fate and toxic effects of trace metals such as mercury (Hg). However, because of limits in DOM analytical techniques and lack of sample diversity in past studies, it remains unclear whether the binding strength of DOM complexed with Hg(II) is related to the DOM properties. In this study, different DOM isolates (n = 26) from various sources were used to determine the conditional stability constant (logK) of DOM-Hg complexes using the equilibrium dialysis ligand exchange (EDLE) method. UV–Vis and fluorescence spectrometry were used to evaluate the correlation between logK values and DOM properties, such as chromophoric moieties, aromaticity, and molecular weight. Results demonstrated that the DOM from different sources presented an extensive range of binding strengths to Hg(II), because of their heterogeneous properties. Moreover, DOM chromophores, including aromaticity and molecular weight, are critical indicators of the DOM-Hg affinity in ambient-relevant circumstances. Significantly, higher terrestrial DOM led to greater DOM-Hg affinity. Additionally, this study supports that UV–Vis and fluorescence spectroscopy can be used to estimate DOM composition and its binding strength with Hg(II). Furthermore, the observed relationship between logK and DOM properties provided a possible pathway of explanation for the spatial co-variations between Hg(II) concentrations and DOM characters observed in previous field investigations.

Elevated temperature altered the binding sequence of Cd with DOM in arable soils

Dissolved organic matter (DOM) is one of the most active soil components, which plays pivotal roles in the migration and fate of heavy metals in soils. The interactions of heavy metals with DOM are controlled by the structure and properties of DOM. The changes of temperature have a significant effect on the content and composition of DOM and thus may affect the binding nature of heavy metals with DOM. In the current study, we conducted a 180-d incubation experiment with an arable soil at temperatures of 15, 30 and 45 °C. Fluorescence spectroscopy was used to examine the composition of DOM and two-dimensional correlation spectroscopy was applied to determine the binding intensity and sequence between cadmium (Cd) with DOM. Two humic-like substances (C1, C3) and a protein-like substance (C2) were identified from soil DOM. Elevated temperature changed the characteristic and structure of DOM. The humification degree and aromaticity of DOM increased from 15 °C to 30 °C but decreased at high temperature (45 °C). The alterations in temperature exert no impact on the type of organic functional groups in DOM binding with Cd. However, elevated temperature changed the binding sequence of Cd with DOM fractions. Polysaccharide, phenolic, and aromatic groups exhibited the fastest response to Cd at 15, 30, and 45 °C, respectively. These observations would provide a better understanding on the environmental behavior of Cd in arable soils under the context of global warming.

Investigation of the variations in dissolved organic matter properties and complexations with two typical heavy metals under the influence of biodegradation: A survey of an entire lake

Biodegradation is a key factor determining the properties and metal binding behaviour of dissolved organic matter (DOM). In this study, the contributions of biodegradation to DOM properties and metal binding behaviour in Dongping Lake were explored by using synchronous fluorescence (SF) spectroscopy, two-dimensional correlation spectroscopy (2D-COS) excitation-emission matrix and parallel factor analysis (EEM-PARAFAC). According to the ratio of the fluorescence intensity of different materials to the entire fluorescence intensity (%Fmax), protein-like substances were the main substances of DOM in this lake. The reduction of protein-like substances and the enhancement of humification could be found in the whole lake under the influence of biodegradation. 3 areas (Area A, Area B and Area C) were obtained by principal component analysis (PCA), however, PCA results suggested that DOM properties and sources had some differences in the 3 areas, and DOM bioavailability in Area C was stronger than that in the other 2 areas. With copper (Cu2+) and lead (Pb2+) addition, different substances exhibited various affinities to different metal types. The locations of crosspeaks in asynchronous maps illustrated that protein-like substances were more affiliative with Cu2+, while humic-like substances were bound to Pb2+ earlier. Biodegradation had a conspicuous impact the metal binding ability of DOM in Dongping Lake. The effective quenching constants (LogK) of protein-like substances (protein-like component 2: LogKCu = 3.85 ± 0.23, LogKPb = 3.32 ± 0.23) were higher than those of humic-like substances (humic-like component 3: LogKCu = 3.15 ± 0.02, LogKPb = 2.93 ± 0.17) for both Cu2+ and Pb2+ before biodegradation. When biodegradation was finished, binding ability of humic-like substances was enhanced from 3.15 ± 0.02 to 3.41 ± 0.10 for DOM-Cu and 2.93 ± 0.17 to 3.79 ± 0.15 for DOM-Pb. On a spatial scale, metal binding ability of DOM in Dongping Lake also changed due to the influence of biodegradation. For both DOM-Cu and DOM-Pb, binding ability in south of Dongping Lake was stronger than that in other areas with the end of biodegradation.

Effects of long-term nitrogen addition on dissolved organic matter characteristics in a temperate wetland of Northeast China

Dissolved organic matter (DOM) plays an indispensable role in ecosystem services and functions in wetlands. While most wetlands have undergone increased nitrogen (N) loading due to intensive human activities, the response of DOM characteristics to long-term N addition remains unexplored. In this study, we assessed the changes in dissolved organic carbon (DOC), NH4+, NO3-, dissolved organic N (DON), dissolved total N (DTN), and dissolved total phosphorus (DTP) in surface water and soil pore water at 15 cm depth after 10 years of N addition at four levels (0, 60, 120, and 240 kg N hm−2 year−1) in a freshwater marsh of Northeast China. We also examined the effect of N addition on DOM aromaticity and humification by measuring the specific UV absorbance at 254 nm (SUVA254), the color per C unit (C/C ratio), and the fulvic acid/humic acid ratio (E4/E6 ratio). Our results showed that N addition significantly altered DOM properties, but the direction and magnitude of these changes generally did not vary with the N addition level. During the growing season, DOC, NH4+, NO3-, DON, and DTN concentrations in both surface water and soil pore water were increased by N addition. Accordingly, N addition increased the DOC/DTP and DTN/DTP ratios but decreased the DOC/DTN ratio in surface water and soil pore water. In addition, the SUVA254 value and C/C ratio increased, while the E4/E6 ratio reduced after N addition in surface water and soil pore water, indicating increases in DOM aromaticity and humification. These observations suggest that long-term N addition changes DOM characteristics by causing stoichiometric imbalances and increasing recalcitrant compounds in temperate freshwater wetlands, which may then deteriorate water quality, alter microbial-mediated ecological processes, and impact downstream aquatic ecosystem structures.

Bulk Chemical and Optical Spectroscopy Characterisations of Dissolved Organic Matter Extracted from the Tropical Coastal Sediment

The study of organic matter characterisation in coastal sediment is useful for understanding how dissolved organic matter (DOM) reactivity influences the fate of pollutants in the aquatic environment. However, there is little information available on the structural properties of DOM in coastal sediment. Chemical analysis, UV-Visible (UV-Vis) absorbance, fluorescence, and Fourier-transform infrared (FTIR) spectroscopy were used in this work to characterise and compare the components of water-extractable organic matter (WEOM) fractions from sediment from an estuary, a coastal area, and a port in Peninsular Malaysia, Malaysia. The elemental analysis (H/C and C/N ratios) of the three samples differed, which coincided with the findings of optical indices estimated from UV-Visible and fluorescent spectroscopy analyses. WEOM had an average output of 7.05 to 8.47 mg/L and was very dominating with heavy fraction organic carbon (HFOC). In DOM-KS and DOM-K sediments, the allochthonous component with a high degree of condensation and the aromatic compound was the dominating composition. Meanwhile, the DOM-KT possessed a high autochthonous composition as well as carboxylic and phenolic content. Correlation analysis indicates that the aromaticity index SUVA254 and humification index (HIX) have positive correlations. The combined results of the chemical and spectroscopic analyses indicate that different coastal ecosystems, with the integration of various human and land activities, produce variations in DOM in the coastal area.

Do DOM optical parameters improve the prediction of copper availability in vineyard soils?

Accumulation of copper (Cu) in soils due to the application of fungicides may be toxic for organisms and hence affect winegrowing sustainability. Soil parameters such as pH and dissolved organic matter (DOM) are known to affect the availability of Cu. In this study, we investigated the contribution of chromophoric and fluorescent DOM properties to the prediction of Cu availability in 18 organic vineyard soils in the Bordeaux winegrowing area (France). The DOM parameters, assessed through absorbance and fluorescence analyses, and proxies for Cu availability (total soluble Cu and free ionic Cu2+) were measured in 0.01 M KCl extracts. Total soluble Cu (CuKCl) varied 23-fold while free ionic Cu2+ varied by a factor of 4600 among the soils. DOC concentrations were similar among the soils, but the samples differed in the quality of DOM as assessed by optical spectroscopy. Multilinear regression models with and without DOM quality parameters were investigated to predict Cu availability. The best model for CuKCl successfully explained 83% of variance and included pH, CuT, and two DOM fluorescence quality indices, the FI fluorescence index, which distinguishes between microbial and higher plant origins, and the HIX humification index. For the prediction of Cu2+, pH alone explained 88% of variance and adding DOM parameters did not improve modelling. The two Cu availability proxies were related to pH. This study confirms the prominent role of pH in Cu availability and underlines the importance of DOM quality to better predict Cu solubility.

When Forests Take Over After Land Abandonment: Dissolved Organic Matter Response in Headwater Mountain Streams

Dissolved organic matter (DOM) represents the largest pool of organic carbon in fluvial ecosystems. The majority of DOM in rivers is of terrigenous origin—making DOM composition highly dependent on vegetation cover and soil properties. While deforestation is still a worldwide anthropogenic phenomenon, current land cover change in temperate regions is often characterized by secondary succession processes following the abandonment of agricultural activities including grazing on pasturelands. This results in (secondary) forest expansion with a consequent, time-lagged transformation of soil properties. Predicting the time scale and spatial scale (i.e., location in the catchment: riparian vs. upslope areas) at which such land cover changes affect the terrestrial-aquatic carbon linkage and concomitantly alter properties of fluvial DOM as drivers of carbon cycling in freshwater ecosystems represents a new scientific challenge. In an attempt to identify potential legacy effects of land cover, i.e., reaction delays of fluvial DOM to changes in land cover, we here investigate the influence of specific current and historic (2 decade-old) land cover types on molecularly resolved fluvial DOM composition in headwater mountain streams. Our analysis is based on a scale-sensitive approach weighing in the distance of land cover (changes) to the stream and ultrahigh-resolution mass spectrometric analyses. Results identified the dominance of terrigenous DOM, with phenolic and polyphenolic sum formulae commonly associated to lignins and tannins, in all the studied streams. DOM properties mostly reflected present-day gradients of forest cover in the riparian area. In more forested catchments, DOM had on average higher molecular weight and a greater abundance of O-rich phenols and polyphenols but less aliphatics. Besides the modulation of the DOM source, our results also point to an important influence of photodegradation associated to variation in light exposition with riparian land cover in defining fluvial DOM properties. Despite expectations, we were unable to detect an effect of historic land cover on present-day DOM composition, at least at the investigated baseflow conditions, probably because of an overriding effect of current riparian vegetation.

Density currents affect the vertical evolution of dissolved organic matter chemistry in a large tributary of the Three Gorges Reservoir during the water-level rising period

Reservoirs have boomed for clean energy in recent decades and interrupted the natural river ecosystem severely. Riverine dissolved organic matter (DOM), which regulates aquatic food web dynamics, water quality, and carbon storage, has been significantly impacted by reservoir construction. However, the vertical evolution of DOM properties and its controlling mechanisms in large reservoirs with hydrological management are not well investigated, limiting the understanding of carbon cycling (e.g., CO2 emissions and carbon burial) in reservoirs. To fill this knowledge gap, multiple complementary techniques including optical spectroscopy and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry were applied to track composition and property changes of DOM along the vertical profile in a large deep tributary of the world largest Three Gorges Reservoir (TGR) during the water-level rising period. The results indicated that middle and bottom water have relatively more terrestrial input and recalcitrant DOM, while surface water has relatively more autochthonous input and labile DOM. Integrated with the comprehensive analysis of DOM chemistry in a high-resolution vertical profile, the primary production and photodegradation in surface water, the density currents induced water intrusion from mainstream to tributaries, in middle water, and the biodegradation in bottom water are main factors controlling the vertical heterogeneity of reservoir DOM during the water-level rising period. This vertical increase of DOM recalcitrance likely contributes to the enhancement of organic carbon burial in TGR during the water-level rising period. All in all, this study provides new insight into the vertical variations of riverine DOM induced by reservoir construction, and emphasizes the important role of reservoir construction in carbon sequestration.

Optical properties of dissolved organic matter highlight peatland-like properties in a constructed wetland

Constructing novel peatland ecosystems can help to restore the long-term carbon accumulating properties of northern soil systems that have been lost through resource extraction. Although mining companies are legally required to restore landscapes following extraction, there are limited tools to evaluate the effectiveness of restoring peat accumulating landscapes. This study analyzed the spatial patterns of the first seven years (n = 575) of dissolved organic matter (DOM) optical characteristics from a pilot watershed built to restore boreal plains peatlands on a former open pit oil sands mine. A principal component analysis (PCA) indicated a very high degree of redundancy in absorption-florescence DOM properties (PARAFAC, HIX, FI, freshness index, SUVA, and peak A, B, C, T, wavelength, and intensity ratios) at this site. The leading principal component indicated a gradient of fresh protein rich inputs, which are highest near the upland region, to older highly degraded DOM, which is highest in the lowland closest to the outlet. Two functionally different reference peatlands, a poor-fen and bog system and a moderate-rich fen, had relatively similar optical DOM characteristics indicating a high level of decomposition at these sites. Over the first seven years, in some regions of the reconstructed lowland the DOM characteristics are becoming increasingly similar to the highly decomposed DOM observed at the reference sites. When combined with carbon flux measurements these findings indicate the potential for long term organic matter accumulation at this reconstructed site.

Dynamic relationship between dissolved organic matter and soluble microbial products during wastewater treatment

Dynamics of the dissolved organic matter (DOM) and soluble microbial products (SMP) significantly affected the sustainability of wastewater treatment plants and effluent qualities. In this study, the origin, transformation, and seasonal variation of DOM components in the anaerobic/anoxic/oxic (A2O) units were illustrated with fluorescence analysis. Results show that the anaerobic process transformed humic acid-like substances (HA) and SMP into fulvic acid-like substances (FA) and aromatic proteins (AP), which indicated the decomposition of macromolecules. In cold seasons, the anoxic process turned AP to HA, SMP, and FA; but the oxic process reversed the transformation. In warm seasons, 6.0% of AP decreased while 3.1% of HA, 1.8% of SMP, and 1.0% of FA increased during the oxic process. Proteobacteria strains were isolated from the activated sludge to stimulate the SMP generation, it was found higher temperature facilitated the transformation of FA and HA (humics) to SMP and AP (proteins), which resulted more proteins presented in the wastewater DOM. These findings indicated that the treatment efficiency and DOM quality in A2O processes were influenced by influent quality and/or temperature conditions, and highlighted the generation of SMP by sludge microorganisms, based on which the corresponding strategies considering the seasonal DOM/SMP dynamics were recommended for the stringent regulation of effluents and the sustainability of the receiving water bodies. Besides, the overall fluorescence intensity was positively correlated with the quantified biopolymer contents in SMP, implying the potential of using the fluorescence-derived information to indicate more quantified DOM properties.

Characterization of Dissolved Organic Matter and Its Derived Disinfection Byproduct Formation along the Yangtze River.

The Yangtze River basin covers one-fifth of China's land area and serves as a water source for one-third of China's population. During long-distance water transport from upstream to downstream, various sources of dissolved organic matter (DOM) lead to considerable variation in DOM properties, significantly impacting water treatability and disinfection byproduct (DBP) formation after chlorination. Using size-exclusion chromatography and fluorescence spectroscopy, the spatial variation in DOM characteristics was comprehensively investigated on a basin scale. The formation of 36 DBPs and speciated total organic halogen in chlorinated samples was determined. Overall, the Yangtze River waters featured a high proportion of terrestrially derived humic substances that served as important precursors for trihalomethanes and haloacetic acids, which was responsible for the increase in total DBP formation along the Yangtze River. The downstream waters were characterized by high levels of microbially derived protein-like biopolymers, which significantly contributed to the formation of haloacetaldehydes and haloacetonitriles that dominated DBP-associated mammalian cell cytotoxicity. Moreover, the precursors of haloacetaldehydes and haloacetonitriles in downstream waters were highly hydrophilic, posing a challenge for water treatment. This study presents an extensive basin-scale study, providing insights into DOM variations along the Yangtze River, illustrating the impact of DOM properties on drinking water from a DBP perspective.

Relationships between the Physicochemical Properties of Dissolved Organic Matter and Its Reaction with Sodium Borohydride.

The reaction of dissolved organic matter (DOM) with sodium borohydride has been used to understand the geographic origin of DOM and investigate the photophysical model underlying DOM's optical properties. However, the physicochemical properties of DOM (e.g., molecular size and charge) that influence the kinetics and ultimate reducibility of DOM by borohydride remain poorly characterized. Herein, we studied the kinetics of DOM-borohydride reactions by recording absorbance and fluorescence spectra at a high temporal frequency (every ∼10 min for 24 h) for a diverse set of DOM isolates of aquatic and soil origin. The reducibility of DOM by sodium borohydride (as judged by relative removal of initial absorbance) varied appreciably among the DOM samples studied, with soil humic substances being less reducible than aquatic humic substances and natural organic matter. While statistically significant correlations were found between the reducibility of DOM and descriptors of molecular size, these descriptors were not able to differentiate the reducibility of soil versus aquatic DOM isolates that had similar bulk properties. Thus, it appears that the extent of absorbance removal by borohydride is largely driven by the origin of the humic substance isolate (aquatic vs soil) instead of molecular size or charge. Borohydride reduction resulted in increased fluorescence emission across UV and visible excitation wavelengths. However, the enhanced emission at visible excitation decreased over a time period of hours to days, suggesting that reduction of an important subset of DOM chromophores is reversible. This reversibility in fluorescence emission is consistent with the small role of quinones in the absorbance of DOM but suggests a more important role for quinone-containing charge-transfer contacts in the fluorescence of DOM, particularly at visible excitation wavelengths.

Ultrafast Energy Transfer Determines the Formation of Fluorescence in DOM and Humic Substances.

Humification is a ubiquitous natural process of biomass degradation that creates multicomponent systems of nonliving organic matter, including dissolved organic matter (DOM) and humic substances (HS) in water environments, soils, and organic rocks. Despite significant differences in molecular composition, the optical properties of DOM and HS are remarkably similar, and the reason for this remains largely unknown. Here, we employed fluorescence spectroscopy with (sub)picosecond resolution to elucidate the role of electronic interactions within DOM and HS. We revealed an ultrafast decay component with a characteristic decay lifetime of 0.5-1.5 ps and spectral diffusion originating from excitation energy transfer (EET) in the system. The rate of EET was positively correlated to the fraction of aromatic species and tightness of aromatic species packing. Diminishing the number of EET donor-acceptor pairs by reduction with NaBH4 (decrease of the acceptor number), decrease of pH (decrease of the electron-donating ability), or decrease of the average particle size by filtration (less donor-acceptor pairs within a particle) resulted in a lower impact of the ultrafast component on fluorescence decay. Our results uncover the role of electronic coupling among fluorophores in the formation of DOM and HS optical properties and provide a framework for studying photophysical processes in heterogeneous systems of natural fluorophores.

Insight into interactions of heavy metals with livestock manure compost-derived dissolved organic matter using EEM-PARAFAC and 2D-FTIR-COS analyses

Dissolved organic matter (DOM), as the most active ingredient in compost, directly determines the speciation and environmental behavior of HMs. Here, the binding properties of DOM derived from chicken-manure compost (CHM), cow-manure compost (COM) and pig-manure compost (PIM) with HMs were explored by analyses of Fluorescence excitation-emission matrix parallel factor (EEM-PARAFAC) and two-dimensional correlation Fourier transform infrared spectroscopy (2D-FTIR-COS). Results showed that the binding characteristics vary with origin of DOM and type of HMs. The fulvic-like component dominated the transformation of HMs speciation, and CHM-DOM had higher affinity with HMs and greater risk causing pollution due to its higher aromaticity, molecular weight and distribution of fluorescent components. Moreover, Cu(II) can efficiently bind to DOM with the stability constants (log kM) ranging from 4.53 to 5.38, followed by Pb(II) (3.34–3.57), whereas Cd(II) can hardly bind to DOM. The amide and polysaccharide were the predominant sites for HMs binding in CHM-DOM, and polysaccharide and phenolic in COM-DOM, while phenolic and amide in PIM-DOM, respectively. Although the proportion of protein-like components and non-fluorescent polysaccharides in DOM were low, their role in HMs binding should not be ignored. In brief, the environmental risk caused by livestock manure compost may originate from interactions between DOM and HMs.