Resolving the variability of CDOM fluorescence to differentiate the sources and fate of DOM in Lake Taihu and its tributaries (original) (raw)

Characterization of CDOM in saline and freshwater lakes across China using spectroscopic analysis

Water Research, 2018

China were examined to determine relationships between lake water sources (fresh versus saline) and their fluorescence/absorption characteristics. Results indicated significant differences regarding DOC concentration and a CDOM (254) between freshwater (6.68 mg C L-1 , 19.55 m-1) and saline lakes (27.4 mg C L-1 , 41.17 m-1). While humic-like (F 5) and fulvic-like (F 3) compounds contributed to CDOM fluorescence in all lake waters significantly, their contribution to total fluorescence intensity (F T) differed between saline and freshwater lakes. Significant negative relationships were also observed between lake altitude with either F 5 (R 2 =0.63, N=306) or F T (R 2 =0.64, N=306), suggesting that the abundance of humic-like materials in CDOM tends to decrease with increased in lakes altitude. In high-altitude lakes, strong solar irradiance and UV exposure may have induced photo-oxidation reactions resulting in decreased abundance of humic-like substances and the formation of low molecular weight compounds. These findings have important implications regarding our understanding of C dynamics in lacustrine systems and the contribution of these ecosystems to the global C cycle.

Spatial-seasonal dynamics of chromophoric dissolved organic matter in Lake Taihu, a large eutrophic, shallow lake in China

Organic Geochemistry, 2011

From 2005 to 2009, the spatial distribution and the seasonal dynamics of chromophoric dissolved organic matter (CDOM) were explored in Lake Taihu in eastern China. The spatial-seasonal dynamics of CDOM absorption and three CDOM composition variables, including spectral slope (S), spectral slope ratio (S R ) and the M value, defined as the ratio of absorption at 250 nm/365 nm, were analyzed and discussed. Furthermore, river input processes and degradation of phytoplankton were studied to assess their impact on CDOM composition and the factors involved in the spatial-seasonal variability of CDOM. The CDOM absorption coefficient at a wavelength of 350 nm, a(350), ranged from 1.37-9.55 m À1 with a mean of 3.33 ± 1.32 m À1 . Spatially, higher a(350) values, but lower spectral slope, spectral slope ratio and M values, were recorded in the northern algae dominated bays while lower values were recorded in southeastern macrophyte dominated bays. The a(350) was significantly higher in inshore waters than in offshore waters. Values of S, S R and M decreased during the flood and algal bloom season in spring and summer whereas a(350) increased. In the three river profiles, the gradual decrease of a(350) along the trajectory from the river mouth into the lake during the flood season showed the contribution of allochthonous CDOM. A laboratory phytoplankton degradation experiment was conducted to determine the contribution of CDOM production from phytoplankton. The significant increase of a(350) with time in the CDOM production experiment underlines the importance of autochthonous CDOM production during the algal bloom season. In summary, the significant increase of a(350) in spring and summer (algal bloom season) may be due to both the allochthonous CDOM input from the surrounding rivers and the autochthonous production of CDOM from degrading phytoplankton.

Dynamics of chromophoric dissolved organic matter influenced by hydrological conditions in a large, shallow, and eutrophic lake in China

Environmental science and pollution research international, 2015

High concentrations of chromophoric dissolved organic matter (CDOM) are terrestrially derived from upstream tributaries to Lake Taihu, China, and are influenced by hydrological conditions of the upstream watershed. To investigate how the dynamics of CDOM in Lake Taihu are influenced by upstream inflow runoff, four sampling cruises, differing in hydrological conditions, were undertaken in the lake and its three major tributaries, rivers Yincun, Dapu, and Changdou. CDOM absorption, fluorescence spectroscopy, chemical oxygen demand (COD), and stable isotope δ(13)C and δ(15)N measurements were conducted to characterize the dynamics of CDOM. The mean absorption coefficient a(350) collected from the three river profiles (5.15 ± 1.92 m(-1)) was significantly higher than that of the lake (2.95 ± 1.88 m(-1)), indicating that the upstream rivers carried a substantial load of CDOM to the lake. This finding was substantiated by the exclusively terrestrial signal exhibited by the level of δ(13)C...

Spatiotemporal Characterization of Chromophoric Dissolved Organic Matter (CDOM) and CDOM-DOC Relationships for Highly Polluted Rivers

water, 2016

Spectral characteristics of CDOM (Chromophoric dissolved organic matter) in water columns are a key parameter for bio-optical modeling. Knowledge of CDOM optical properties and spatial discrepancy based on the relationship between water quality and spectral parameters in the Yinma River watershed with in situ data collected from highly polluted waters are exhibited in this study. Based on the comprehensive index method, the riverine waters showed serious contamination; especially the chemical oxygen demand (COD), iron (Fe), manganese (Mn), mercury (Hg) and dissolved oxygen (DO) were out of range of the contamination warning. Dissolved organic carbon (DOC) and total suspended matter (TSM) with prominent non-homogenizing were significantly high in the riverine waters, but chlorophyll-a (Chl-a) was the opposite. The ternary phase diagram showed that non-algal particle absorption played an important role in total non-water light absorption (>50%) in most sampling locations, and mean contributions of CDOM were 13% and 22% in the summer and autumn, respectively. The analysis of the ratio of absorption at 250–365 nm (E250:365) and the spectral slope (S275–295) indicated that CDOM had higher aromaticity and molecular weight in autumn than in summer, which is consistent with the results of water quality and the CDOM relative contribution rate. Redundancy analysis (RDA) indicated that the environmental variables OSM (Organic suspended matter) had a strong correlation with CDOM absorption, followed by heavy metals, e.g., Mn, Hg and Cr6+. However, for the specific UV absorbance (SUVA254), the seasonal values showed opposite results compared with the reported literature. The potential reasons were that more UDOM (uncolored dissolved organic matter) from human sources (wastewater effluent) existed in the waters. Terrigenous inputs simultaneously are in relation to the aCDOM(440)-DOC relationship with the correlation coefficient of 0.90 in the summer (two-tailed, p < 0.01), and 0.58 in the autumn (two-tailed, p < 0.05). Spatial distribution of the CDOM parameters exhibited that the downstream regions focused on dry land have high CDOM molecular weight and aromatic hydrocarbon. Partial sampling locations around the cities or countries generally showed abnormal values due to terrigenous inputs. As a bio-optical model parameter, the spectral characteristic of CDOM is helpful in adjusting the derived algorithms in highly polluted environments. The study on organic carbon and pollutants in highly polluted waters had an important contribution to global carbon balance estimation and water environment protection.

Characterization of Chromophoric Dissolved Organic Matter (CDOM) in Rainwater Using Fluorescence Spectrophotometry

Bulletin of Environmental Contamination and Toxicology, 2011

The fluorescence excitation-emission matrix of Chromophoric dissolved organic matter (CDOM) samples from rainwater collected at Rameswaram, Tamilnadu, India are analysed. Total five peaks were observed for humic/marine and protein likes substances respectively. The peak A and C intensities varies form 1.98 ± 0.28 and 0.97 ± 0.11 QSU respectively represents humic like substances. The peak B and T intensities varies from 3.94 ± 0.75 and 7.42 ± 1.43 QSU showed association of protein like substances whereas peak M intensities varies from 1.92 ± 0.37 QSU indicates marine contribution. Among the fluorophores, the following sequence were observed as T [ B [ A [ M [ C which indicates dominance of Tryptophan like substances in rainwater. The average peak T/C ratios was observed as 7.88 ± 2.2 indicates microbial contamination by Tryptophan-like substances with the high biological activity and low volatility. Keywords CDOM Á Fluorescence intensities Á HIX Á BIX Chromophoric organic matter (CDOM), an optically active component of DOM, plays an important role in carbon cycling and affects ocean color (Hong et al. 2005; Coble 2007). It is present in fresh or saltwater primarily due to the release of tannins (polyphenols that bind to proteins and other large molecules) or lignins (polymers of phenolic acids) by decaying plant material. CDOM may also be characterized as byproducts from the decomposition of animals. Water color may range from pale yellow to brown as a result of varying concentrations and sources of CDOM. The presence of significant quantities of highly CDOM in atmospheric waters has profound ramifications with respect to a wide variety of fundamental processes in atmospheric chemistry because of its impact on solar radiative transfer and its involvement in the oxidizing and acid generating capacity of the troposphere. Additionally, if CDOM constituents are surface-active they will have a direct impact on droplet population and consequently cloud albedo by lowering the surface tension of atmospheric waters. CDOM, which is the fraction of DOM that absorbs light over a broad range of ultraviolet (UV) and visible wavelengths, is essentially controlled by in situ biological production, terrestrial inputs (sources), photochemical degradation, microbial consumption (sinks), as well as deep ocean circulation (Coble 2007; Para et al. 2010).

Characterization of CDOM in reservoirs and its linkage to trophic status assessment across China using spectroscopic analysis

Journal of Hydrology, 2019

Chromophoric dissolved organic matter (CDOM) represents the optically active component of the DOM pool, and originates from both allochthonous and autochthonous sources. The fluorescent characteristics of dissolved organic matter (FDOM) has been widely used to trace CDOM sources and infer its composition. However, little is known about the optical and fluorescent properties of CDOM in drinking water reservoirs, and the variability of CDOM properties along trophic gradients in these aquatic systems. A total of 536 water samples were collected between 2015 and 2017 from 131 reservoirs across China to characterize CDOM and FDOM properties using both light absorption and fluorescence spectroscopies, and examine relationships with water-quality condition as expressed by the modified trophic state index (TSI M) of the reservoirs (range: 12 < TSI M < 78). With increased reservoir trophic status, CDOM absorption coefficients at 254 nm (a CDOM (254)) and total fluorescence of FRI-EEMs (excitation-emission matrix coupled with fluorescence regional integration) increased significantly (p < 0.01). Our results indicated that the nutrients in aquatic systems and the social economy factors (including wastewater, sewage, cultivated land, GDP, population) and altitude affect the CDOM absorption and fluorescence significantly (p < 0.05). Most importantly, we proposed a new classification standard associated with eutrophic status via CDOM humification index (HIX) due to the significant correlation between each other (p < 0.01). HIX less than 4 was corresponding to TSI M less than 30 as oligotrophic states; 4 < HIX ≤ 12 was corresponding to TSI M less than 50 as mesotrophic states; 12 < HIX ≤ 18 was corresponding to TSI M less than 70 as eutrophic states; HIX more than 18 is defined as hypereutrophic status with TSI M > 70. This method highlights the importance of CDOM fluorescence for aquatic DOM input and strengthens the linkage between the trophic status index and CDOM characteristics, it also contributes to establish a new rapid assessing model with quick experimental measurements to monitor the trophic status of water reservoirs.

Characterization of CDOM in an organic-rich river and surrounding coastal ocean in the South Atlantic Bight

Aquatic Sciences - Research Across Boundaries, 2003

Variability in chromophoric dissolved organic carbon (CDOM) was characterized in and around the Cape Fear River and Onslow Bay, North Carolina USA. The river end member of the study region are extremely rich in CDOM, thus the Cape Fear River serves as a point source of CDOM-rich water into the southeastern Atlantic bight. The river plume is easily traceable and generally extends in a southwesterly direction along the coastline into Long Bay. Depending on physical processes and river flow, the plume can meander somewhat and may even turn northward for short periods of time. The oceanic end member of this study was the Gulf Stream. Samples from the Gulf Stream were obtained up to 97 km off shore. The experimental approach focused on the qualitative and quantitative description of CDOM from fresh-to-oceanic waters. CDOM was characterized by excitation emission matrix (EEM) fluorescence and UV/VIS spectroscopy. Variability of CDOM absorption in the relatively small area of the Cape Fear River estuary and surrounding coastal ocean was very high. The observed range of variability of CDOM absorption coeffi- Aquat. Sci. 65 (2003) 381 -398 cient, a CDOM (350), extended over nearly the entire range of CDOM absorption in the literature: 0.046 = a CDOM (350) = 29.9 m -1 . Changes in CDOM absorption spectrum slope coefficient S, were small in the Cape Fear River plume area, but relatively large in Onslow Bay. CDOM EEM spectra indicated that a radical change in composition of CDOM occurs along the river-to-oceanic salinity gradient. CDOM in the coastal ocean was characterized by strong reduction of the three principal intensity peaks: A, C, and M, and a prominent contribution of the T peak to the fluorescence spectrum. The fluorescence intensity is linearly related with absorption. There is a strong inverse relationship between salinity and CDOM absorption, however our data show that this relationship may be dependent on river flow. The distribution of the slope coefficient and the percent contribution of respective peak intensities to the total EEM intensity showed that CDOM undergone conservative mixing until it approached oceanic salinity. Thus, CDOM is so concentrated in the river that mixing and other physical processes mask photochemical or biological alteration of its composition.

Comparison of seasonal changes in fluorescent dissolved organic matter among aquatic lake and stream sites in the Green Lakes Valley

Journal of Geophysical Research, 2010

The spectral characteristics of whole water dissolved organic matter (DOM) and fulvic acid were studied in samples collected from an alpine lake, a subalpine lake, and a subalpine stream during snowmelt and the summer growing season. Excitation-emission matrices of whole water DOM and fulvic acid were analyzed by parallel factor analysis (PARAFAC). Allochthonous inputs of terrestrially derived fulvic acid DOM were dominant during snowmelt at the alpine lake, and during both snowmelt and summer at the subalpine sites. At the alpine lake, autochthonous inputs of DOM dominated during the summer phytoplankton bloom, and the spectral characteristics of the whole water DOM diverged from those of the fulvic acid. For example, the quinone-like fluorophores in whole water DOM at the alpine lake were more oxidized and microbially derived than the fulvic acid fraction during the summer. At the subalpine sites, the seasonal changes in the source and redox state of the quinone-like fluorophores of the whole water DOM tracked those of the fulvic acid pool. However, at both lake sites there was a greater contribution of amino acid-like fluorophores in the whole water DOM than the fulvic acid fraction. This trend was not observed at the subalpine stream site. Principal components analysis (PCA) of the PARAFAC components suggests that during snowmelt, the chemical quality of the DOM at the alpine lake was similar to that of the subalpine stream; whereas the alpine site was more similar to the subalpine lake during the summer. Spectral characterization and PCA of the PARAFAC components suggest that nonhumic quinone-like and amino acid-like fluorophores were produced in the alpine lake during the summer phytoplankton bloom. Our results show that different types of water bodies produce different seasonal patterns in whole water DOM and fulvic acid quantity and quality.

Absorption and fluorescence properties of chromophoric dissolved organic matter: implications for the monitoring of water quality in a large subtropical reservoir

Environmental Science and Pollution Research, 2014

The development of techniques for real-time monitoring of water quality is of great importance for effectively managing inland water resources. In this study, we first analyzed the absorption and fluorescence properties in a large subtropical reservoir and then used a chromophoric dissolved organic matter (CDOM) fluorescence monitoring sensor to predict several water quality parameters including the total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD), dissolved organic carbon (DOC), and CDOM fluorescence parallel factor analysis (PARAFAC) components in the reservoir. The CDOM absorption coefficient at 254 nm (a(254)), the humic-like component (C1), and the tryptophanlike component (C3) decreased significantly along a gradient from the northwest to the lake center, northeast, southwest, and southeast region in the reservoir. However, no significant spatial difference was found for the tyrosine-like component (C2), which contributed only four marked peaks. A highly significant linear correlation was found between the a(254) and CDOM concentration measured using the CDOM fluorescence sensor (r 2 =0.865, n=76, p<0.001), indicating that CDOM concentrations could act as a proxy for the CDOM absorption coefficient measured in the laboratory. Significant correlations were also found between the CDOM concentration and TN, TP, COD, DOC, and the maximum fluorescence intensity of C1, suggesting that the real-time monitoring of CDOM concentrations could be used to predict these water quality parameters and trace the humic-like fluorescence substance in clear aquatic ecosystems with DOC <2 mg/L and total suspended matter (TSM) concentrations <15 mg/L. These results demonstrate that the CDOM fluorescence sensor is a useful tool for on-line water quality monitoring if the empirical relationship between the CDOM concentration measured using the CDOM fluorescence sensor and the water quality parameters is calibrated and validated.

Fluorescence characterization of fractionated dissolved organic matter in the five tributaries of Poyang Lake, China

The Science of the total environment, 2018

Characterization of natural colloids is the key to understand pollutant fate and transport in the environment. The present study investigates the relationship between size and fluorescence properties of colloidal organic matter (COM) from five tributaries of Poyang Lake. Colloids were size-fractionated using cross-flow ultrafiltration and their fluorescence properties were measured by three-dimensional excitation-emission matrix fluorescence spectroscopy (3D-EEM). Parallel factor analysis (PARAFAC) and/or Self-organizing map (SOM) were applied to assess fluorescence properties as proxy indicators for the different size of colloids. PARAFAC analysis identified four fluorescence components including three humic-like components (C1-C3) and a protein-like component (C4). These four fluorescence components, and in particular the protein-like component, are primarily present in <1 kDa phase. For the colloidal fractions (1-10 kDa, 10-100 kDa, and 100 kDa-0.7 μm), the majority of fluorop...