Protein-like Components Research Articles

Characteristics of dissolved organic matter in water bodies during the dry season in the Huainan section of the Huaihe River Basin in Northern Anhui Province, China

This study investigated the spatial heterogeneity of dissolved organic matter (DOM) composition and characteristics in the central reaches of the Huaihe River Basin. The dry season DOM content and composition of three river bodies (the main stream of Huaihe River, the Huaihe tributaries and agricultural drainage ditches) in the Huaihe River Basin were studied using UV-Vis and three-dimensional fluorescence spectroscopy combined with parallel factor analysis (EEMs-PARAFAC). The degree of DOM humification and the relative molecular weight of tributaries and agricultural drainage ditches were significantly higher than those of the main stream (p < 0.01), and regarding the autogenetic characteristics of the three types of water bodies the tributaries and drainage ditches were more strongly affected by exogenous interference than the main stream. Three kinds of chemical components were determined by PARAFAC mode(C1:terrsstrial humus-like;C2:tryptophan-like;C3:protein-like), protein-like components were the main fluorescent components in DOM during the dry season, the proportion of different water systems exceeds 50%. Principal component analysis (PCA) showed that the fluorescence intensity of humus was closely related to the TP(Total phosphorus) concentration in the Huainan section water body of the Huaihe River Basin during the dry season. The absolute principal component-multiple linear regression model showed that the contribution of water nutrition to the C2 and C3 of protein-like fluorescent components was greater, while exogenous interference had a greater effect on the TP physicochemical index.

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.

Utilizing fluorescence indicators to apportion organic sources in estuarine/coastal sediments: A comparison with a stable isotopic model

Coastal sediments accumulate organic matter (OM) from diverse sources, including local anthropogenic pollution. Effective source tracking of sediment OM is crucial for pollution source management. This study compares fluorescence proxies and stable isotopic ratios as tracers for sediment OM in Gangu Port, Korea. An optimized extraction method using distilled water for 0.5 h yielded distinct fluorescence signatures. The humification index (HIX) and protein-like component (C3%) showed ideal mixing behavior with two end-members (fishery market sediment and algae). A Bayesian end-member mixing analysis model revealed that agricultural soil is the prevalent contributor to sediments, aligning with land use patterns. The fluorescence-based model showed higher sensitivity to anthropogenic influences compared to traditional stable isotope ratios. The results strongly agreed with isotope ratio-based predictions, exhibiting a positive correlation (p < 0.05) at 8 out of 14 sites. This study highlights the potential of fluorescence-based tracking to complement or replace conventional stable isotope methods.

Scallop farming impacts on dissolved organic matter cycling in coastal waters: Regulation of the low molecular weight fraction

To elucidate the impacts of scallop farming on the biogeochemical characteristics of low molecular weight (LMW, <1 kDa) dissolved organic matter (DOM), samples collected from a bay scallop mariculture area (MA) and its surrounding areas were determined for absorption and fluorescence spectroscopy after microfiltration and centrifugal ultrafiltration. The values of absorption coefficient a350 showed a spatial variation trend of inshore area (IA) > MA > non-mariculture area (NMA) for both bulk (<0.7 μm) and LMW fractions. Four fluorescent components, namely two protein-like components (tryptophan-like C1 and tyrosine-like C2) and two humic-like components (microbial humic-like C3 and terrestrial humic-like C4), were identified. Scallop farming influenced DOM transformation by altering phytoplankton abundance and promoting microbial degradation. In July, the net contributions of phytoplankton to the spectroscopy parameters of LMW-DOM in the surface seawater were 11.0% for a350, 4.3% for C1, 0.8% for C2, 0.6% for C3 and 3.0% for C4, respectively; the corresponding values of bulk DOM in the surface seawater were 24.3% for a350, 20.1% for C1, 5.9% for C2, 2.0% for C3, 2.9% for C4, respectively. Compared with NMA, the contributions of microbial degradation to a350 in MA's surface seawater increased by 9.0% for LMW-DOM and 6.9% for bulk DOM in July; however, the effects on different fluorescent components varied. In August, compared with NMA, the contributions of microbial degradation to spectroscopy parameters in the bottom water of MA decreased by 35.7% for a350, 6.3% for C2, 1.3% for C3, and 4.4% for C4 for LMW-DOM fraction; for bulk DOM, the corresponding contribution decreased by 10.8% for C1. These variations indicate that protein-like substances from scallop aquaculture are easily degraded into LMW substances, while humic-like substances degradation diminishes over time.

Using physicochemical properties to predict the impact of natural dissolved organic carbon on transepithelial potential in the freshwater rainbow trout (Oncorhynchus mykiss) at neutral and acidic pH.

Dissolved organic carbon (DOC) is a complex mixture of molecules that varies in composition based on origin as well as spatial and temporal factors. DOC is an important water quality parameter as it regulates many biological processes in freshwater systems, including the physiological function of the gills in fish. These effects are often beneficial, especially at low pH where DOCs mitigate ion loss and protect active ion uptake. DOCs of different compositions and quality have varied ionoregulatory effects. The molecular variability of DOCs can be characterized using optical and chemical indices, but how these indices relate to the physiological effects exerted by DOCs is not well understood. We tested the effects of five naturally sourced DOCs, at both pH 7 and pH 4, on transepithelial potential (TEP) (a diffusion potential between the blood plasma and the external water) in rainbow trout. The five chosen DOCs have been well characterized and span large differences in physicochemical characteristics. Each of the DOCs significantly influenced TEP, although in a unique manner or magnitude which was likely due to their physicochemical characteristics. These TEP responses were also a function of pH. With the goal of determining which physicochemical indices are predictive of changes in TEP, we evaluated correlations between various indices and TEP at pH 7 and pH 4. The indices included: specific absorbance coefficient at 340nm, molecular weight index, fluorescence index, octanol-water partition coefficient, molecular charge, proton binding index, % humic acid-like, % fulvic acid-like, and % protein-like components by parallel factor analysis on fluorescence data (PARAFAC). Our results demonstrate the novel finding that there are three particularly important indices that are predictors of changes in TEP across pHs in rainbow trout: specific absorbance coefficient at 340nm, octanol-water partition coefficient; and proton binding index.

Long-term rice-crayfish farming alters soil dissolved organic carbon quality and biodegradability by regulating microbial metabolism and iron oxidation

The biodegradability of dissolved organic carbon (DOC) is a crucial process in the migration and transformation of soil organic carbon (SOC), and play a vital role in the global soil carbon (C) cycle. Although the significance of DOC in SOC transportation and microbial utilization is widely acknowledged, the impact of long-term rice-crayfish (RC) farming on the content, quality, and biodegradability of DOC in paddy soils, as well as regulatory mechanisms involved, remains unclear. To address this gap, a space-for-time method was employed to investigate the effects of different RC farming durations (1-, 5-, 10-, 15-, and 20- years) on the quality and biodegradability of DOC, as well as their relationship with soil microbial metabolism and minerals in this study. The results revealed that continuous RC farming increased the soil DOC content, but reduced DOC biodegradability. Specifically, after 20 years of continuous RC farming, the DOC content increased by 52.7% compared to the initial year, whereas the DOC biodegradability decreased by 63.4%. Analysis using three-dimensional fluorescence and ultraviolet spectroscopy demonstrated that continuous RC farming resulted in a decrease in the relative abundance of humus-like fractions, humification, and aromaticity indexes in DOC, but increased the relative abundance of protein-like fractions, biological, and fluorescence index, indicating that long-term RC farming promoted the simple depolymerization of the molecular structure of DOC. Continuous RC farming increased the activity of hydrolase involved in soil nitrogen (N) and phosphorus (P) cycles and oxidase, but decreasing the hydrolase C/N and C/P acquisition ratios; moreover, it also stimulated an increase in soil iron oxides and exchangeable calcium content. Structural equation modeling suggests that soil hydrolases and iron oxides are the primary drivers of DOC quality change, with DOC biodegradability being driven solely by soil iron oxides and not regulated by DOC quality. In conclusion, long-term RC farming promotes the catalytic decomposition of DOC aromatic substances and the production of DOC protein-like components by increasing soil oxidase activity and decreasing the hydrolase C/N acquisition ratio; these processes collectively contribute to the simple depolymerization of DOC molecular structure. Additionally, long-term RC farming induced legacy effects of soil iron oxides and enhanced chemical protection role leading to reduced DOC biodegradability. These findings suggested that long-term RC farming may reduce the rapid turnover and loss of DOC, providing a negative feedback on climate warming.

Impacts of an intensive traditional mariculture model on offshore environments as evidenced by dissolved organic matter and bacterial communities

Mariculture is a key protein source and economic driver but traditional methods pollute coastal waters, hindering sustainable development. Current research on the ecological impacts of mariculture mainly focuses on specific pollutants and lacks an assessment of the biogeochemical impacts of mariculture discharge. This study examined Xiangshan Bay, a representative intensive mariculture area in China, to explore the impact of mariculture tailwater discharge on water quality, focusing on dissolved organic matter (DOM) and bacterial communities. Based on the fluorescence excitation-emission matrix combined with parallel factor analysis, a characteristic fluorescence component C4 was identified in mariculture tailwater (intensity of 40 ± 4 %, n = 8), while higher C4 components (47 ± 3 %, n = 15) were found throughout the bay. Humic-like components from riverine input (C1 + C2: 32 ± 3 %, n = 15) and protein-like components from domestic sewage (C5: 2 ± 1 %, n = 15) were significantly lower in the seawater samples, indicating the strong influence of mariculture tailwater on the entire DOM structure of the bay. The bacterial community structure showed a response consistent with DOM, as revealed by nonmetric multidimensional scaling analysis. This showed that bacterial communities in mariculture tailwater and bay water samples clustered together, independent of riverine input. The SourceTracker model indicated that mariculture tailwater (91 ± 5 %) predominantly contributed to the bacterial community, with minimal contributions from riverine input (< 5 %). Co-occurrence network analysis further showed that under long-term high-intensity mariculture discharge, the C4 component became the core DOM and was closely associated with the bacterial community. The results here demonstrate the profound impact of traditional mariculture on coastal water quality and show that riverine input is not the primary pollution source in this region, providing clear directions for coastal environmental restoration efforts.

A comparative study of optical and size properties of dissolved organic matter in the lower Mississippi River and Pearl River

Monthly water samples were collected from the lower Mississippi and Pearl Rivers between January 2009 and August 2011 to investigate the heterogeneity in the dynamic variations of dissolved organic carbon (DOC), colloidal organic carbon, chromophoric and fluorescence dissolved organic matter (CDOM and FDOM), PARAFAC-derived fluorescent components, and other optical properties including spectral slope, specific UV absorbance (SUVA), and fluorescence indices between the two contrasting river systems. The lower Mississippi River exhibits relatively lower concentrations of DOC (306 ± 41 μM C) and CDOM (27.9 ± 5.7 m−1 at 254 nm), featuring lower aromaticity (indicated by SUVA254) and apparent molecular weight (or higher spectral slope) with weak seasonal variability. The Pearl River, in contrast, has elevated levels of DOC (537 ± 212 μM C) and CDOM (66.4 ± 31.4 m−1), characterized by higher aromaticity, higher molecular weight, and significant seasonality, primarily originating from soil-derived allochthonous sources. The abundance of the >1 kDa colloidal DOC was, on average, 58 ± 3 % of the bulk DOC in the lower Mississippi River and 68 ± 6 % in the lower Pearl River. The >1 kDa high-molecular weight DOM (HMW-DOM) consistently had lower spectral slope and biological index (BIX) values, but higher humification index (HIX) values compared to both bulk DOM and low-molecular-weight DOM (LMW-DOM) counterparts. These trends could be representative of other similar large and small rivers. Four PARAFAC-derived fluorescent components (three humic-like and one protein-like) were identified for both rivers. A positive correlation between discharge and terrestrial humic-like fluorescent components indicated their dominant allochthonous sources, while the protein-like component decreased with increasing discharge, consistent with its autochthonic source and a dilution effect during high flow seasons. The occurrence of large flood events during the sampling period contributed to large DOC pulses, with DOM of higher aromaticity and HMW-DOM. This has important implications for coastal ocean ecosystems, which are increasingly impacted by river flooding events under changing climate conditions. Our results also provide an improved understanding of DOM dynamics in two representative rivers and establish a baseline dataset for future studies to assess changes in sources and composition of DOM and their impacts on the coastal ocean in response to climate, hydrological, and anthropogenic influences.

Land Use Cover and Flow Condition Affect the Spatial Distribution Characteristics of Fluorescent Dissolved Organic Matter in the Yongding River

Dissolved organic matter (DOM) is involved in many biogeochemical processes and plays an important role in aquatic ecosystems. This study integrated three-dimensional fluorescence excitation–emission matrix (EEM), fluorescence regional integration (FRI), and parallel factor analysis (PARAFAC) to better understand the distribution and component characteristics of DOM in the Yongding River and explore the response of DOM to natural and anthropogenic activities. The results showed that the relative abundance of fulvic-like materials of DOM in the river was the highest, with an average of 68.64%. PARAFAC identified three fluorescent components, namely, C1 (microbial humic-like components), C2 (terrestrial humic-like components), and C3 (protein-like components), and their changes with flow confirmed that the riverine DOM was generally influenced by microbial sources and terrestrial inputs. The upper reaches showed strong autochthonous characteristics and a high humification degree of DOM due to a fast flow rate, while the middle reaches showed biological or aquatic bacterial origin due to a moderate flow rate. The lower reaches of the river showed characteristics of biological and bacterial origin, most strongly influenced by human activities. The findings can help provide a basis for identifying DOM characteristics in the Yongding River basin and understanding the geochemical cycle of DOM at a regional scale.

Spectral Characteristics of Dissolved Organic Matter in Sediments from Yuanhe River Basin

Dissolved organic matter （DOM） plays an important role in indicating the pollution of the water environment, and sediment is the main source of endogenous pollution of the water environment. Research on the spectral characteristics of DOM in sediments was important for the interpretation of water environment pollution. In this study, UV-visible absorption spectroscopy and three-dimensional fluorescence spectroscopy combined with the parallel factor analysis （PARAFAC） were used to analyze the fluorescent components, sources, and influencing factors of DOM in sediments from the Yuanhe River Basin. The results showed that the average of ω（TN）, ω（TP）, and ω（OM） in sediments from the Yuanhe River Basin were 0.52, 0.66, and 21.22 g·kg-1, respectively. The concentrations of total nitrogen and total phosphorus increased along the flow direction. In addition, the sediment DOM from the Yuanhe River Basin mainly originated from terrestrial sources. The chromophoric DOM concentration and aromaticity of DOM from the downstream reaches were significantly higher than those from the upstream and midstream reaches. Based on PARAFAC, four fluorescent components of DOM in sediments from the Yuanhe River Basin were identified, including three humus-like components （C1, C3, and C4） and one protein-like component （C2）. The sediment DOM was dominated by humus-like materials. Moreover, the fluorescent intensity of the fluorescent components was higher in the downstream reaches. Redundancy analysis revealed that the physicochemical properties of sediments in the mainstream and downstream reaches played a more significant role in the spectral properties of DOM. Phosphorus pollution and the terrestrial humus-like substance of sediment DOM were homologous. These results indicated that the spectral properties of DOM were the indicator of water environmental pollution in the region with strong anthropogenic influence.

Microbial nitrogen nutrition links to dissolved organic matter properties in East African lakes

East African lakes, especially soda lakes, are home habitats for massive numbers of wildlife such as flamingos, mammals, and fishes. These lakes are known for their high primary production due to local high temperatures, light intensities, and alkalinity (inorganic carbon). However, these lakes, normally within remote areas, receive low nutrient inputs. Ammonium (NH4+) recycling and/or nitrogen fixation can become the major N supply mechanisms for phytoplankton. However, the driving forces on microbial N nutrition in lakes with minimal anthropogenic disturbance remain poorly understood. Using stable isotope tracer techniques, NH4+ recycling rates were measured in 18 lakes and reservoirs in East Africa (Tanzania and Kenya) during the dry season in early 2020. Three functional genes (nifH, gdh, and ureC) relating to microbial N nutrition were also measured. The regeneration of NH4+ supported up to 71 % of the NH4+ uptake. Positive community biological NH4+ demands (CBAD) for all lakes and reservoirs indicate an obvious N demand from microbial community. Our study provides clear evidence that microbial NH4+ uptake rates linked closely to the dissolved organic matter (DOM) properties (e.g., the absorption coefficient at 254 nm, percents of total fluorescence intensity contributed by microbial humic-like and protein-like components) and that water residence time drives microbial NH4+ recycling by regulating the duration of in-lake DOM processing and influencing algal growth. Phytoplankton, especially those of Cyanophyceae, showed maximum biomass and higher NH4+ recycling rates at a certain range of water residence time (e.g., 5–8 years). However, CBAD showed a decreasing trend with longer water residence time, which may be influenced by changes in the algal community composition (e.g., % Cyanophyceae vs. % Bacillariophyceae). These results indicate that DOM dynamics and the water residence time have the potential to facilitate the understanding of microbial nitrogen supply status in East African lakes.

Effects of photodegradation on the composition characteristics and metal binding behavior of sediment-derived dissolved organic matter (SDOM) in nansi lake, China

Sediment-derived dissolved organic matter (SDOM) is instrumental in the cycling of nutrients and heavy metals within lakes, influencing ecological balance and contaminant distribution. Given the influence of photodegradation on the alteration and breakdown of SDOM, further understanding of this process is essential. In this research, the properties of the SDOM photodegradation process and its metal-binding reactions in Nansi Lake were analyzed using the EEM-PARAFAC and 2D-SF/FTIR-COS techniques. Our study identified three sorts of humic-like components and one protein-like component in SDOM, with the humic-like material accounting for 71.3 ± 5.19% of the fluorescence intensity (Fmax). Photodegradation altered the abundance and structure of SDOM, with a 41.6 ± 5.82% decrease in a280 and a 29.1 ± 9.31% reduction in Fmax after 7 days, notably reducing the protein-like component C4 by 54.0 ± 5.17% and the humic-like component C2 by 48.5 ± 2.54%, which led to SDOM being formed with lower molecular weight and aromaticity. After photodegradation, the LogKCu values for humic-like and protein-like substances decreased (humic-like C2: LogKCu: 1.35 ± 0.10–1.11 ± 0.15, protein-like C4: 1.49 ± 0.14–1.29 ± 0.34), yet the preferential binding sequence of protein-like materials and specific functional groups with Cu2+ such as aliphatic C-OH, amide (I) C=O and polysaccharide C-O groups remained unaltered. Our results enhance the knowledge of light-induced SDOM alterations and offer insights into SDOM-metal interactions in aquatic ecosystems.

Identifying the fate of dissolved organic matter in wastewater treatment plant effluent-dominated urban river based on fluorescence fingerprinting and flux budget approach

Effluent organic matter from wastewater treatment plants (WWTPs) is an important source of dissolved organic matter (DOM) in urban rivers worldwide and is an important water quality factor. Identifying the fate of DOM in urban river is crucial for water quality management. To address this concern, a fluorescent flux budget approach was conducted to probe the fate of DOM in WWTP effluent-dominated urban river, in combination with field measurement and fluorescence fingerprinting. An urban river receiving two WWTP effluents in Hefei City, China was chosen as the study site, where longitudinal measurements of river hydrology and water quality were performed. The fluorescence fingerprinting revealed the presence of two humic-like components (C1, C4), one fulvic-like component (C2) and one protein-like component (C3) in this investigated river, among which C2 and C4 were indicative of anthropogenic influences, closely associated with treated effluents. For each fluorescent component, the WWTP effluent contributed over 80 % of the total fluorescent dissolved organic matter (FDOM) input in this river. Using the developed FDOM flux budget model, it was found that the C1 and C3 were almost conserved within the waterbody, while the C2 and C4 experienced losses due to biogeochemical reactions. The decay rates of C2 and C4 were estimated to be 0.109–0.174 d−1 and 0.096–0.320 d−1, respectively. Spatial heterogeneity of decay rates for C2 and C4 were associated with the varied chemistries of the lateral input sources including two treated effluents and one tributary flow. Our study highlights that after treated effluent is released into the receiving waterbody, the FDOM would undergo loss from the waters particularly for anthropogenic fulvic-like substance C2 and humic-like substance C4. Additionally, the quantified FDOM decay rate in actual urban water environment provides insights for river water quality management, especially when using DOM as the surrogate indicator of organic pollutants.

Natural Attenuation of Groundwater Uranium in Post-Neutral-Mining Sites Evidenced from Multiple Isotopes and Dissolved Organic Matter.

Although natural attenuation is an economic remediation strategy for uranium (U) contamination, the role of organic molecules in driving U natural attenuation in postmining aquifers is not well-understood. Groundwaters were sampled to investigate the chemical, isotopic, and dissolved organic matter (DOM) compositions and their relationships to U natural attenuation from production wells and postmining wells in a typical U deposit (the Qianjiadian U deposit) mined by neutral in situ leaching. Results showed that Fe(II) concentrations and δ34SSO4 and δ18OSO4 values increased, but U concentrations decreased significantly from production wells to postmining wells, indicating that Fe(III) reduction and sulfate reduction were the predominant processes contributing to U natural attenuation. Microbial humic-like and protein-like components mediated the reduction of Fe(III) and sulfate, respectively. Organic molecules with H/C > 1.5 were conducive to microbe-mediated reduction of Fe(III) and sulfate and facilitated the natural attenuation of dissolved U. The average U attenuation rate was -1.07 mg/L/yr, with which the U-contaminated groundwater would be naturally attenuated in approximately 11.2 years. The study highlights the specific organic molecules regulating the natural attenuation of groundwater U via the reduction of Fe(III) and sulfate.

Estimation of net accumulation and removal of fluorescent dissolved organic matter in different Baltic Sea water masses

This study aimed to detect non-conservative processes that affect the distribution of fluorescent dissolved organic matter (FDOM) in the Baltic Sea. An extensive data set comprised of 408 FDOM data, optical and physical profiles, and the development of a water masses balance model allowed us to ascertain the sources of mixing anomalies. These were seen as second-order deviations in the FDOM distribution as a function of salinity in three layers: surface water, Baltic Sea Winter Water, and deep water. The difference between modeled and measured FDOM values at three different excitation/emission wavelengths allowed to show the strength of non-conservative processes, such as photochemical and microbial decomposition (negative residual values) or extracellular release of dissolved organic matter from phytoplankton, heterotrophic uptake and release from anoxic sediments (positive residual values). Humic-like FDOM fractions displayed positive residuals in all seasons for intermediate and deep layers and negative residuals in surface waters. Largest accumulation rates of humic-like fractions were reached in the Gulf of Gdańsk during summer in intermediate and deep layers, while the greatest removal in surface waters was observed during spring in the Bornholm and Gotland Basins and during summer in the Gulf of Gdańsk, probably due to photodegradation. Positive residuals of the protein-like fraction were observed at the surface in summer and autumn in the Gulf of Gdańsk, probably linked to the abundance of phytoplankton and also due to the low molecular weight by-products of photodegradation of humic-like components. Spatial transects revealed an increase in humic-like residuals with depth and a strong correlation with apparent oxygen utilization, increasing with higher fluorescence and exhibiting an asymptotic trend. A relationship was found between the protein-like fractions and phytoplankton biomass proxies. A generalized concept for FDOM cycling in the Baltic Sea was proposed, highlighting photobleaching as the dominant non-linear process determining the efficiency of humic-like FDOM removal. The protein-like component was found to be more efficiently taken up by aerobic prokaryotes at the surface. Microbial utilization and reworking of organic matter, release from sediments, and a decade-long stagnation of bottom water masses, all contribute to the observed accumulation of FDOM in mesohaline deep waters below the permanent pycnocline in the Baltic Sea.

Insights into the characteristics of changes in dissolved organic matter fluorescence components on the natural attenuation process of toluene

Natural attenuation (NA) is of great significance for the remediation of contaminated groundwater, and how to identify NA patterns of toluene in aquifers more quickly and effectively poses an urgent challenge. In this study, the NA of toluene in two typical soils was conducted by means of soil column experiment. Based on column experiments, dissolved organic matter (DOM) was rapidly identified using fluorescence spectroscopy, and the relationship between DOM and the NA of toluene was established through structural equation modeling analysis. The adsorption rates of toluene in clay and sandy soil were 39 % and 26 %, respectively. The adsorption capacity and total NA capacity of silty clay were large. The occurrence of fluorescence peaks of protein-like components and specific products indicated the occurrence of biodegradation. Arenimonas, Acidovorax and Brevundimonas were the main degrading bacteria identified in Column A, while Pseudomonas, Azotobacter and Mycobacterium were the main ones identified in Column B. The pH, ORP, and Fe(II) were the most important factors affecting the composition of microbial communities, which in turn affected the NA of toluene. These results provide a new way to quickly identify NA of toluene.

Effects of Tryptophan and Tyrosine on the Transformation of Monophenols in Chromophoric Dissolved Organic Matter Solutions: Enhance the Forward Transformation and Reduce the Reverse Transformation.

Tryptophan (Trp) and tyrosine (Tyr) are the primary precursors of protein-like components in dissolved organic matter. Phenolic compounds are ubiquitous in aquatic environments and are considered the main electron donor in chromophoric dissolved organic matter (CDOM). Our results showed that Trp and Tyr (50 μM) enhanced the transformation of six monophenols (20 μM) with varying numbers of -CH3 and -OCH3 substituent groups by a factor of 1.0-1.8. The enhancement factor increased with the ratio of Trp (Tyr) to monophenols. In four different CDOM solutions (5 mg C/L, pH 8.0), a maximum enhancement factor of 3.2-6.7 was observed at a Trp/monophenol concentration ratio of 50. Conversely, monophenols greatly inhibited the transformation of Trp or Tyr. The enhancement factor decreased as the initial pH increased from 3.0 to 10.0. Additionally, the enhancement factor was not directly proportional to the oxidation potential of monophenol. We propose that the promotion effects are generated through the direct oxidation of monophenols by Trp (Tyr) radicals as well as through the reaction between Trp (Tyr) radicals and the one-electron reductant of CDOM.

Deciphering dissolved organic matter characteristics and its fate in a glacier-fed desert river—the Tarim river, China

The bioavailable diverse dissolved organic matter (DOM) present in glacial meltwater significantly contributes to downstream carbon cycling in mountainous regions. However, the comprehension of molecular-level characteristics of riverine DOM, from tributary to downstream and their fate in glacier-fed desert rivers remains limited. Herein, we employed spectroscopic and high-resolution mass spectrometry techniques to study both optical and molecular-level characteristics of DOM in the Tarim River catchment, northwest China. The results revealed that the DOC values in the downstream were higher than those in the tributaries, yet they remained comparable to those found in other glacier-fed streams worldwide. Five distinct components were identified using EEM-PARAFAC analysis in both tributary and downstream samples. The dominance of three protein-like components in tributary samples, contrasting with a higher presence of humic-like components in downstream samples, which implied that the dilution and alterations of the glacier DOM signature and overprinting with terrestrial-derived DOM. Molecular composition revealed that thousands of compounds with higher molecular weight and increased aromaticity were transformed, generated and introduced from terrestrial inputs during downstream transportation. The twofold rise in polycyclic aromatic and polyphenolic compounds observed downstream compared to tributaries indicated a greater influx of terrestrial organic matter introduced into the downstream during water transportation. The study suggests that the glacier-sourced DOM experienced minimal photodegradations, with limited influence from human activities, while also being shaped by terrestrial inputs during its transit in the alpine-arid region. This unique scenario offers valuable insights into comprehending the fate of DOM originating from glacial meltwater in arid mountainous regions.

Hydrodynamics and dissolved organic matter components shaped the fate of dissolved heavy metals in an intensely anthropogenically disturbed estuary

Anthropogenic activities and natural erosion caused abundant influx of heavy metals (HMs) and organic matter (OM) into estuaries characterized by the dynamic environments governed by tidal action and river flow. Similarities and differences in the fate of HM and OM as well as the influences of OM on HMs remain incomplete in estuaries with seasonal human activity and hydrodynamic force. To address this gap, dissolved HMs (dHMs) and fluorescence dissolved OM (FDOM) were investigated in the Pearl River Estuary, a highly seasonally anthropogenic and dynamic estuary. It aimed to elucidate the effects of hydrodynamic conditions and DOM on the seasonal fate of dHMs via the multivariate statistical methods. Our findings indicated dHMs and FDOM exhibited consistently higher levels in the upper estuarine and coastal waters in both seasons, predominantly controlled by the terrestrial/anthropogenic discharge. In the wet season, dHMs and humic-like substances (HULIS) were positively correlated, showing that dHMs readily combined with HULIS. This association led to a synchronous decrease offshore along the axis of the estuary and the transport following the river plume in the surface affected by the salt wedge. Contrarily, dHMs were prone to complex with protein-like components impacted by the hydrodynamics during the dry season. Principal component analysis (PCA) results revealed the terrestrial/anthropogenic inputs and the fresh-seawater mixing process were the most crucial factors responsible for the fate of dHM in wet and dry seasons, respectively, with DOM identified as a secondary but significant influencing factor in both seasons. This study holds significance in providing valuable insights into the migration, transformation, the ultimate fate of dHMs in anthropogenically influenced estuaries, as well as the intricate dynamics governing coastal ecosystems.

Fluorescence spectroscopy for tracking microbiological contamination in urban waterbodies

Dissolved organic matter (DOM) plays a crucial role in freshwater ecosystem function. Monitoring of DOM in aquatic environments can be achieved by using fluorescence spectroscopy. Particularly, DOM fluorescence can constitute a signature of microbiological contamination with a potential for high frequency monitoring. However, limited data are available regarding urban waterbodies. This study considers fluorescence data from field campaigns conducted in the Paris metropolitan region: two watercourses (La Villette basin and the river Marne), two stormwater network outlets (SO), and a wastewater treatment plant effluent (WWTP-O). The objectives of the study were to characterize the major fluorescence components in the studied sites, to investigate the impact of local rainfall in such components and to identify a potential fluorescence signature of local microbiological contamination. The components of a PARAFAC model (C1-C7), corresponding to a couple of excitation (ex) and emission (em) wavelengths, and the fluorescence indices HIX and BIX were used for DOM characterization. In parallel, fecal indicator bacteria (FIB) were measured in selected samples. The PARAFAC protein-like components, C6 (ex/em of 280/352 nm) and C7 (ex/em of 305/340 nm), were identified as markers of microbial contamination in the studied sites. In the La Villette basin, where samplings covered a period of more than 2 years, which also included similar numbers of wet and dry weather samples, the protein-like components were significantly higher in wet weather in comparison to dry weather. A positive relationship was obtained between C6 and FIB. In urban rivers, the high frequency monitoring of C6 levels would support the fecal contamination detection in rivers. In addition, it could help targeting specific field campaigns to collect comprehensive dataset of microbiological contamination episodes.