Riverine carbon (C) composition and export are closely related to changes in the coastal environment and climate. Excessive C inputs from rivers to seas and their subsequent decomposition could result in harmful algal blooms and ecosystem degradation in the coastal sea. In this study, we explored the C transportation and composition in the 24 major rivers of the Bohai Sea (BS) Rim based on the investigation of dissolved organic carbon (DOC), carbon stable isotopes (δ¹³CDOC) and chromophoric dissolved organic matter (CDOM). The results showed that the riverine DOC concentrations were high (10.6 ± 6.04 mg/L) in the BS Rim compared with the DOC levels in the main rivers in Eastern China (4.98 ± 2.45 mg/L). The δ¹³CDOC ranged from −28.29‰ to −25.32‰ in the rivers of the BS Rim, suggesting that the DOC mainly originated from riverine plankton, soil organic matter mainly induced by C3 plants, and sewage. The excitation-emission matrix fluorescence spectroscopy of the CDOM indicated that a soluble, microbial by product-like material accounted for the largest proportion (approximately 40%) of CDOM in these rivers and that CDOM mainly originated from autochthonous riverine sources with high protein-like components. The rivers in the BS Rim transported approximately 0.55 Tg C of DOC to the BS each year, with more than 70% of reactive C based on the CDOM composition. The DOC yields in terms of unit drainage area transported from the small rivers to the BS were higher compared to those of the larger rivers in the world, which indicated that the small rivers in the Bohai Rim could be an important source of the C in the BS. This study would enrich our understanding of environmental evolution in coastal areas with numerous small rivers.

In peri-urban critical zones, soil ecosystems are highly affected by increasing urbanization, causing probably an intense interaction between dissolved organic matter (DOM) and heavy metals in soil. Such interaction is critical for understanding the biogeochemical cycles of both organic matter and heavy metals in these zones. However, limited research has reported the correlative distribution of DOM and heavy metals at high seasonal and spatial resolutions in peri-urban critical zones. In this study, 160 soil samples were collected from the farmland and forestland of Zhangxi watershed, in Ningbo, eastern China during spring, summer, fall and winter four seasons. UV–visible absorption and fluorescent spectroscopy were used to explore the optical characteristics of DOM. The results indicated a mixture of exogenous and autogenous sources of DOM in the Zhangxi watershed, while DOM in farmland exhibited a higher degree of aromaticity and humification than that in forestland. Fluorescent results showed that humic acid-like, fulvic acid-like and microbial-derived humic-like fractions were mostly affected by seasons. The distribution of heavy metals was affected mainly by land-use changes and seasons. Correlation analysis between heavy metals and DOM characteristics and components suggested that aromatic and humic substances were more favorable in binding with EDTA extractable Ni, Cu, Zn and Cd. The bioavailable Cd and Pb decreased due to binding with humic fractions, indicating its great effects on the bioavailability of Cd and Pb. Overall, these findings provide an insight into the correlative distributions of DOM and heavy metals in peri-urban areas, thereby highlighting their biogeochemical cycling in the soil environment.

Per- and polyfluoroalkyl substances (PFASs) have been found to be widely present in soil. Dissolved organic matter (DOM) in soil are supposed to greatly affect the bioavailability of PFASs in soil. Herein, hydroponic experiments were conducted to understand the impacts of two kinds of typical DOM, bovine serum albumin (BSA) and humic acid (HA), on the uptake and translocation of legacy PFASs and their emerging alternatives, perfluorooctane sulfonic acid (PFOS), perfluorooctane acid (PFOA), perfluorohexane sulfonic (PFHxS) and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFESA) in wheat (Triticum aestivum L.). The results indicated that both HA and BSA significantly inhibited the bioaccumulation and translocation of PFASs in the roots and shoots of wheat, and the impacts of BSA were greater than HA. This difference was explained by the greater binding affinities of the four PFASs with BSA than with HA, as evidenced by the equilibrium dialysis and isothermal titration calorimetry (ITC) analyses. It was noting that inhibition impacts of the BSA-HA mixture (1:1) were lower than BSA alone. The results of Fourier transform infrared (FT-IR) spectroscopy and excitation-emission matrix (EEM) fluorescence spectroscopy suggested that HA could bind with the fluorescent tryptophan residues in BSA greatly, competing the binding sites with PFASs and forming a cover on the surface of BSA. As a result, the binding of PFASs with BSA-HA complex was much lower than that with BSA, but close to HA. The results of this study shed light on the impacts of DOM in soil on the bioaccumulation and translocation of PFASs in plants.

Despite the wide applications of end member mixing analysis (EMMA) for assigning the sources of dissolved organic matter (DOM) in aquatic environment, there was no study attempting to test the applicability of EMMA for predicting environmental reactivity of DOM. This study aimed to explore the feasibility of EMMA, or the concept of ideal mixing behavior of end members, for describing several well-known DOM reactivities using two DOM end member sources (i.e., soil and algae) at varying mixing ratios. The selected DOM reactivities were trihalomethane formation potential (THMFP), mineral adsorption amount, pyrene binding, membrane resistance, and biodegradation potential. Among the tested DOM functions, all were found to follow the ideal mixing behavior, presenting the linear relationships between the source mixing ratios and the tested reactivity with the R² value of >0.80. The ideal mixing behavior of the DOM functions was more pronounced than that based on several spectroscopic indicators derived from UV absorption and fluorescence spectroscopy. This study provided insight into potential applicability and limitation of EMMA approach in monitoring and predicting environmental functions of DOM in aquatic systems where identified DOM sources are mixed and vary dynamically with the mixing ratios.

Fluorescence spectroscopy is a commonly used technique to analyze dissolved organic matter in aquatic environments. Given the high sensitivity and non-destructive analysis, fluorescence has recently been used to study water-soluble organic carbon (WSOC) in atmospheric aerosols, which have substantial abundance, various sources and play an important role in climate change. Yet, current research on WSOC characterization is rather sparse and limited to a few isolated sites, making it challenging to draw fundamental and mechanistic conclusions. Here we presented a review of the fluorescence properties of atmospheric WSOC reported in various field and laboratory studies, to discuss the current advances and limitations of fluorescence applications. We highlighted that photochemical reactions and relevant aging processes have profound impacts on fluorescence properties of atmospheric WSOC, which were previously unnoticed for organic matter in aquatic environments. Furthermore, we discussed the differences in sources and chemical compositions of fluorescent components between the atmosphere and hydrosphere. We concluded that the commonly used fluorescence characteristics derived from aquatic environments may not be applicable as references for atmospheric WSOC. We emphasized that there is a need for more systematic studies on the fluorescence properties of atmospheric WSOC and to establish a more robust reference and dataset for fluorescence studies in atmosphere based on extensive source-specific experiments.

Dissolved organic matter (DOM) is recognized as a good indicator of water quality as its concentration is influenced by land use, rainwater, windborne material and anthropogenic activities. Recent technological advances make it possible to characterize fluorescent dissolved organic matter (FDOM), the fraction of DOM that fluoresces. Among these advances, portable fluorometers and benchtop fluorescence excitation and emission spectroscopy coupled with a parallel factor analysis (EEM-PARAFAC) have shown to be reliable. Despite their rising popularity, there is still a need to evaluate the extent to which these techniques can assess DOM dynamics at the watershed scale. We compare the performance of in-situ measurements of FDOM with laboratory measurements of fluorescence spectroscopy within the context of two distinct glacierized watersheds in Peru. Glacierized watersheds represent unique testing environments with contrasting DOM conditions, flowing from pristine, vegetation-free headwaters through locations with obvious anthropogenic influences. We used an in-situ fluorometer and a portable multimeter to take 38 measurements of FDOM, pH and turbidity throughout the two catchments. Additionally, samples were analyzed in the laboratory using the EEM-PARAFAC method. Results were compared to dissolved organic carbon (DOC) measurements using standard high-temperature catalytic oxidation. Our results show that the three techniques together were able to capture the DOM dynamics for both studied watersheds. Taken individually, all three methods allowed detection of the watershed DOM main points of sources but in a more limited way. Due to the narrow bandwidth of the portable fluorometer used in the study, FDOM measurements were almost non-detectable to protein-like substances. Indeed, the more demanding EEM-PARAFAC was able to both differentiate between potential sources of DOM and provide an estimate of relative concentrations of different organic components. Finally, similar to FDOM but to a lesser extent, the DOC measurements showed some limits where protein-like substances make up most of the DOM composition.

A novel denitrifying bacterium YSF15 was isolated from the Lijiahe Reservoir in Xi’an and identified as Comamonas sp. It exhibited excellent nitrogen removal ability under low C/N conditions (C/N = 2.5) and 94.01% of nitrate was removed in 18 h, with no accumulation of nitrite. PCR amplification and nitrogen balance experiments were carried out, showing that 68.92% of initial nitrogen was removed as gas products and the nitrogen removal path was determined to be NO3−-N→NO2−-N→NO→N2O→N2. Scanning electron microscopy and three-dimensional fluorescence spectroscopy were used to track extracellular polymeric substances (EPS). The results show that complete-denitrification under low C/N conditions is associated with EPS, which may provide a reserve carbon source in extreme environments. These findings reveal that Comamonas sp. YSF15 can provide novel basic materials and a theoretical basis for wastewater bioremediation under low C/N conditions.

Nanoparticles (NPs), heavy metal and natural organic matter (NOM) may simultaneously exist in the aquatic environment, where they will affect the behavior of each other and may enhance their toxicities. Studies on the influences of interactions between NOM and heavy metal ions on the behavior of NPs are scarce. In this study, combined effects of Pb²⁺ and HA on the aggregation behavior of TiO₂ NPs in water environment were investigated by Dynamic light scattering (DLS) and Nanoparticle tracking analysis (NTA). The results illustrated that interactions between Pb²⁺ and HA could case the aggregation of TiO₂ NPs obviously. The concurrence of Pb²⁺ and HA resulted in decreased critical coagulation concentration (CCC) and increased attachment efficiencies. Meanwhile, we found that the addition sequences of HA and heavy metal clearly influenced the aggregation kinetics of TiO₂ NPs. At different addition sequences, the complex reaction between Pb²⁺ and HA changed the surface charge of TiO₂ NPs, and caused the different aggregation behavior which depended on the complex locations and complex sites. Furthermore, the excitation-emission-matrix (EEM) fluorescence spectra was used to verify the significant effects of the complex interactions between Pb²⁺ and HA on the aggregation of TiO₂ NPs. Our results would be significant for interpreting TiO₂ behavior in the complicated water system.The complexation between Pb²⁺ and HA promoted the aggregation of TiO₂ NPs, meanwhile, complex locations and complex sites played an important role.

Widely used titanium dioxide (TiO2) nanoparticles are likely to accumulate ultimately in sediments and potentially pose a risk to water ecosystems. This study evaluated the effect of TiO2 nanoparticles on the photodissolution of particulate organic matter (POM) through fluorescence spectroscopy. Excitation-emission matrices and parallel factor analyses revealed that the fluorescent characteristics of produced dissolved organic matter (DOM) during photodissolution of suspended sediment and synthetic particulate organic matter (SPOM) were primarily humic-like. SPOM particles appeared to simulate well the photodissolution of suspended sediment. Quasi-complete increases in fluorescence intensity and chromophoric DOM (CDOM) abundance were reached after 90, 60, and 50 min irradiation for TiO2 concentrations of 0, 2, and 5 mg L−1, respectively. The faster increment of fluorescence intensity and CDOM abundance indicated the photocatalytic dissolution of SPOM, as opposite charges between TiO2 and SPOM at pH = 4 favored the adsorption of TiO2 onto SPOM. For sediments, the CDOM abundance and fluorescence intensity decreased with increasing TiO2 concentration, resulting from the photocatalytic degradation of photoproduced DOM from sediments. These results demonstrated that pH plays an important role in the photocatalytic dissolution of POM by TiO2. Therefore, appropriate pH controls should be implemented when TiO2 are used to treat sediments contaminated with organic pollutants. Finally, with increasing use of TiO2, its accumulation in sediments may affect the fate of carbon, nutrients, and heavy metals in shallow-water ecosystems.

Dissolved organic carbon (DOC) plays diverse roles in carbon biogeochemical cycles. Here, we explored the link between DOC and pCO2 using high-performance size-exclusion chromatography (HPSEC) with UV254 detection and excitation emission matrix (EEM) fluorescence spectroscopy to determine the molecular weight distribution (MW) and the spectral characteristics of DOC, respectively. The relationship between DOC and pCO2 was investigated in the Poyang Lake wetlands and their adjacent aquatic systems. The results indicated significant spatial variation in the DOC concentrations, MW distributions, and pCO2. The DOC concentration was higher in the wetlands than in the rivers and lakes. pCO2 was high in wetlands in which the dominant vegetation was Phragmites australis, whereas it was low in wetlands in which Carex tristachya was the dominant species. DOC was divided into five fractions according to MW, as follows: super-low MW (SLMW, <1 kDa); low MW (LMW, 1–2.5 kDa); intermediate MW (IMW, 2.5–3.5 kDa); high MW (HMW, 3.5–6 kDa); and super-high MW (SMW, > 40 kDa). Rivers contained high proportions of HMW and extremely low amounts of SLMW, whereas wetlands had relatively high proportions of SLMW. The proportion of SMW (SMWp) was particularly high in wetlands. We found that pCO2 significantly positively correlated with the proportion of IMW, and significantly negatively correlated with SMWp. These data improve our understanding of the MW of bioavailable DOC and its conversion to CO2. The present results demonstrate that both the content and characteristics of DOC significantly affect pCO2. pCO2 and DOC must be studied further to help understanding the role of the wetland on the regional CO2 budget.