Chromophoric Dissolved Organic Matter Composition Research Articles

Increased dominance of terrestrial component in dissolved organic matter in Chinese lakes

The source composition of chromophoric dissolved organic matter (CDOM) in lakes is closely related to regional environmental changes, human activities, and the carbon cycle. The spectral slope ratio (SR) is an important parameter of CDOM optical components, and combined with remote sensing technology, the source composition of CDOM can be tracked comprehensively and efficiently in large regions. Here, we proposed a CDOM source tracking remote sensing model (CDOM-SR) based on the hue angle (α) to assess the spatial pattern and long-term trend of the CDOM source composition in Chinese lakes (surface area ≥ 1 km2) from 1986 to 2021. Validation results show that the CDOM-SR model has a good SR estimation performance with a median absolute percentage difference, root mean square deviation, median ratio, and median deviation of 17.91 %, 0.23, 1.02, and 0.03, respectively. We found that the average SR of Chinese lakes presents an obvious spatial pattern of high in the west and low in the east due to the difference in human activity intensity and the natural geographical environment. Additionally, we found that the average SR of Chinese lakes from 1986 to 2021 decreased at a rate of - 0.06/10 years, of which 64.37 % of lakes decreased significantly, 15.42 % of lakes had no significant change, and only 20.20 % of lakes increased. The widespread decrease in the average SR indicates that the increasing human activity discharge of terrestrial organic matter has had an important impact on the source composition of the CDOM in Chinese lakes. Our results provide a new resource for remote sensing monitoring of CDOM sources and important insights into lake carbon cycling under the influence of ongoing human activities.

Water quality, basin characteristics, and discharge greatly affect CDOM in highly turbid rivers in the Yellow River Basin, China

Significant variations exist in water quality parameters and inherent optical properties (IOPs) in highly turbid rivers. For rivers in the Yellow River (YR) Basin, 83.33% of the collected samples exhibited high turbidity, and the absorption of non-algal particles (NAPs) was the main contributor to total water absorption. In this study, we investigated the compositions of chromophoric dissolved organic matter (CDOM) using the absorption index and fluorescence components, examined the quantitative effects of environmental factors on CDOM at the sub-basin scale and identified where and how carbon was produced in the area. The humic-like component (FR5) of CDOM was the main component in the tributaries and the main stream of the YR, especially for the Huangshui River, with FR5 accounting for 58.12%. Water quality parameters greatly affected CDOM in turbid rivers. Dissolved organic carbon and electrical conductivity were positively correlated with the CDOM concentration (p < 0.05), while dissolved oxygen, pH, chlorophyll-a and turbidity significantly affected CDOM composition (p < 0.01). Basin characteristics exerted significant influences on CDOM. The spectral slope (S275-295) increased as the altitude of the sub-basins increased. The percentage of built-up area exerted the most significant effects on CDOM composition, with high correlations with tryptophan-like protein (FR2) and FR5 (r > 0.59, p < 0.01). Forest percentage and grassland percentage showed positive correlations with CDOM concentration (r = 0.36, p < 0.05) and S275-295 (r = 0.30, p < 0.05), respectively. Moreover, the discharge from rivers in the YR Basin showed that the carbon flux of rivers in the YR Basin is more likely to be limited by dissolved organic matter (DOM) sources although negative but nonsignificant effects of discharges on CDOM parameters were shown. Consequently, additional research is necessary to clarify this correlation. This research is crucial and necessary for improving the accuracy of CDOM evaluation with remote sensing, revealing the influencing mechanisms and monitoring carbon cycling.

Emission of Methane from a Key Lake in the Eastern Route of the South-to-North Water Transfer Project and the Corresponding Driving Factors

Lakes play an important role in the biogeochemical cycling of dissolved organic matter (DOM) and the emission of methane (CH4). We investigated the concentration and effluxes of CH4 and then analyzed the corresponding driving factors in Lake Luoma, a key lake along the South-to-North Water Transfer Project. Our results indicated that Lake Luoma was a hotspot of CH4 emissions with an annual mean concentration and efflux of (0.12±0.09) μmol·L-1 and (21.0±18.5) mmol·(m2·d)-1, respectively. We found higher mean CH4 levels in the wet season than those in the dry season and further higher levels than those in the wet-to-dry transition season. Spatially, the CH4 efflux was higher in the northwest inflowing regions and lower in the southeast outflow regions. The variability in annual CH4 efflux was affected by a combination of water temperature and hydrological conditions. Terrestrial input of dissolved organic carbon (DOC) and chromophoric DOM (CDOM) had fueled the production of CH4 by providing necessary carbon substrates, and four PARAFAC DOM components were identified including a microbial humic-like C1, a tryptophan-like C2, a terrestrial humic-like C3, and a tyrosine-like C4. The CH4 efflux from the lake was significantly promoted by the input and accumulation of terrestrial humic-like components, and Chl-a had no correlation with CH4 efflux, suggesting that algal degradation was not directly fueling the emission of CH4. Lake Luoma had been significantly disturbed by human activities, and terrestrial input of nutrient loading (TN and TP) into the lake not only improved the productivity and trophic level of the water body but also enhanced the production and release of CH4 from the surface water. We concluded that the CH4 emissions in Lake Luoma can be influenced by the combination of environmental factors, CDOM composition, and nutrient level. Long-term observation is needed for better evaluation of the driving factors in fueling the emission of CH4 so as to effectively reduce the emissions of CH4 and other greenhouse gases by taking corresponding countermeasures.

Optical Composition and Potential Driving Factors of Chromophoric Dissolved Organic Matter in Large Lakes and Reservoirs in the Eastern Region of China

Intensified urbanization has been occurring in the eastern region of China in recent decades, and excessive industrial and household sewage has been discharged into lakes and reservoirs, which has directly lowered water quality and destructed the functions of aquatic ecosystems. Lakes and reservoirs are typically drinking water sources supplying water for metropolitan areas as well as large- and medium-sized cities. Chromophoric dissolved organic matter (CDOM) is the colored fraction of DOM, and its source and optical composition strongly affect water supply safety and the health of surrounding citizens. In April 2021, we collected 68 samples from Reservoir Changtan (n=11), Lake Taihu (n=25), Lake Hongze (n=18), and Lake Gaoyou (n=14), and we further carried out 28 days of laboratory bio-incubation, together with optical measurements and parallel factor analysis (EEMs-PARAFAC) to analyze the bio-degradability ω(BDOC), sources, and optical composition of CDOM in these waters. The results showed that after 28 days of laboratory bio-incubation, the bioavailability of dissolved organic carbon (BDOC) of the four lakes and reservoirs were all higher than 50%. PARAFAC results showed that CDOM collected from the four lakes was composed of four fluorescent components, including a terrestrial humic-like C1, a tryptophan-like C2, and tyrosine-like C3 and C4. Protein-like components (C2, C3, and C4) contributed importantly to the CDOM pool in the four waterbodies, and in Lake Hongze the contribution of C2-C4 was as high as (90.0±2.2)%. In Lake Hongze, total phosphorus (TP) correlated closely with C1-C3, indicating that those components can be used to trace the variability of TP. Among the four waterbodies, a254 was positively correlated with DOC (R2=0.96, P<0.01), indicating that a254 can be used to estimate the dynamics of DOC in these waters. In Lake Taihu, we found a low level of humification index (HIX) and a high level of biological index (BIX), indicating that autochthonous substances contributed importantly to the CDOM pool in this lake. In comparison, allochthonous sources contributed importantly to the CDOM pool in the remaining three waters. The enhanced monitoring of the discharge of industrial and agricultural effluents in the upstream watersheds of the four waters can help to protect the water quality and maintain healthy aquatic ecosystems.

Photochemical and microbial alteration of chromophoric dissolved organic matter (CDOM) in aquatic ecosystems associated with different sources

城市非点源污染向水生生态系统中输入大量的溶解有机物(DOM)，对生态系统健康产生重要影响. 有色可溶性有机物(CDOM)是广泛分布于自然水体中的一类成分和结构复杂、含有多种高活性化学官能团的大分子聚合物，是DOM的重要组分，对水生生态系统健康、能量流动及生物地球化学循环有重要影响. 光化学反应和微生物代谢过程被认为是控制水体CDOM转化、降解和循环的主要影响因素. 然而，对城市化如何影响CDOM组成以及光化学和微生物如何相互作用影响城市水体CDOM动态的理解是不足的. 因此，为评估光化学过程和微生物代谢对不同城市水体CDOM降解与转化的贡献，解析不同城市水体CDOM光化学/微生物降解作用机理，本研究在英国伯明翰选择3类具有典型DOM来源的水体样本，通过实验室9 d受控培养实验，对比分析光化学以及微生物影响下CDOM来源和组成的变化. 结果表明：(1)城市河流由于接受上游污水排放及较短的水力滞留时间，含有丰富的芳香性碳，其CDOM光化学活性明显高于湖泊，光化学降解率为16.60%;(2)城市湖泊CDOM受人类活动影响，自生源类荧光成分富集，生物活性高，在微生物培养过程中CDOM增加了62.16%，而相较于城市湖泊，非城市湖泊由于接受周围景观土壤输入的大量腐殖质类CDOM，光照对其降解转化作用较为明显; (3)光化学过程促进了陆源CDOM中大分子类腐殖质物质降解成为生物活性高的小分子化合物，刺激微生物代谢生成类蛋白质类有机物; 以类蛋白质组分为主导的CDOM在光照过程中被转化为难降解状态，生物活性降低，CDOM微生物代谢过程被抑制. 研究成果为城市水体不同CDOM来源及活性差异特征研究提供了新的思路，有助于城市河流的可持续开放与管理.;Urban non-point source pollution contributes large amounts of dissolved organic matter (DOM) to aquatic ecosystems and has a significant impact on ecosystem health. Chromophoric dissolved organic matter (CDOM) is a group of macromolecular polymers with complex composition and structure, containing a variety of highly reactive chemical functional groups, which are widely distributed in natural waters. It has an important impact on aquatic ecosystem health, energy flow and biogeochemical cycling. Photochemical reactions and microbial metabolic processes are the main controlling factors on the transformation, degradation and cycling of CDOM in water bodies. However, understanding how urbanization source input impacts CDOM quantity and quality and how photochemical and microbial interact to affect CDOM dynamic are deficient. To assess the contribution of photochemical processes and microbial metabolism to the degradation and transformation of different sources of CDOM in urban waters, and to elucidate the mechanisms of photochemical/microbial degradation of different sources of CDOM in aquatic systems (non-urban lake with humic, mostly terrestrial CDOM; urban lake with autochthonous biological production CDOM; urban river with mixed humic and protein-like CDOM), this study compares and analyses the changes in the sources and composition of CDOM under the influence of photochemistry and microorganisms in a controlled 9-day laboratory incubation experiment in three water bodies with typical urban characteristics, selected in Birmingham, UK. Changes in CDOM concentration, optical properties and chlorophyll concentration were measured at the initial and end of incubations. The results show that: (1) due to the acceptance of upstream sewage discharge and shorter hydraulic retention times, the CDOM of urban rivers is dominated by aromatic substances, with the highest photochemical degradation rate of 16.60%; (2) the CDOM of urban lakes, which is affected by human activities, is dominated by autochthonous substances, and could be increased by 62.16% via microbial metabolism, while compared to urban lakes, non-urban lakes have a more pronounced effect of light on their degradation and transformation due to receiving a large input of humus-like CDOM from the surrounding landscape soils; (3) the photochemical process could degrade terrestrial humic-like substances into small molecular compounds with high biological activity, which could stimulate microbial metabolism to produce protein-like CDOM, however, photochemical degradation could inhibit microbial metabolism by transform the autochthonous protein-like CDOM into a refractory state. The study provides a novel perspective for the differences in the sources and activities of CDOM in different urban aquatic systems and the changes in CDOM characteristics during photochemical and microbial processes.

Inventory of riverine dissolved organic carbon in the Bohai Rim

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.

Characterizing Sources and Composition of Chromophoric Dissolved Organic Matter in a Key Drinking Water Reservoir Lake Tianmu

Lake Tianmu is an important source of drinking water, and its water quality can influence ecosystem service functions. Unraveling the sources and composition of chromophoric dissolved organic matter (CDOM) that can affect water treatment processes is necessary to maintain water supply safety and ecosystem service functioning of Lake Tianmu. Samples were collected monthly in 2017 and analyzed for CDOM absorbance and fluorescent spectra using parallel factor analysis (PARAFAC) to investigate the spatial and temporal variations of CDOM sources and composition in Lake Tianmu. PARAFAC results showed that CDOM in Lake Tianmu was mainly composed of a microbial humic-like component C1 (44.2%±9.8%), followed by a tryptophan-like component C2 (29.2%±4.3%), tyrosine-like component C3 (17.2%±13.1%), and terrestrial humic-like component, C4 was the lowest (9.4%±2.4%). The CDOM abundance a(254) and fluorescence intensities of C1 and C2 were significantly higher in the river mouths than in the downstream lake regions, whereas the spectral slope S275-295 was significantly lower in the river mouths (t-test, P<0.05), indicating that allochthonous inputs cause an elevated degree of humification and relative increase in the molecular weight of CDOM in the inflowing river mouths. Seasonal differences in CDOM composition were mainly ascribed to the a(254) and fluorescence intensities of C1, C2, and C4 being significantly higher in the summer and autumn than in the winter and spring (t-test, P<0.05). Our results showed that the influences of different seasons on CDOM composition comprise differences in rainfall and runoff input, as well as water temperature, thermal stratification, phytoplankton biomass, and mineralization of CDOM by light and microbes.

Sources and compositional characterization of chromophoric dissolved organic matter in a Hainan tropical mangrove-estuary

Chromophoric dissolved organic matter (CDOM) is a major optically active component of DOM in estuaries that plays a significant part in maintaining the ecosystem sustainability of mangrove forests via affecting nutrient and micronutrient ((micro)nutrient) biogeochemical processes and pathways. This study was conducted in Hainan Dongzhai Harbor to better understand the sources, composition, and behaviors of CDOM in a tropical mangrove estuary. Water samples were collected from the upper fluvial mangrove zones to the lower marine endmember along the estuarine salinity gradient and analyzed by absorption and fluorescence spectroscopy combined with parallel factor analysis (PARAFAC). DOC, TDN, TDSi, Mn, Ba, and optical characteristics, i.e., a254, SUVA, HIX, and the abundance of humic-like CDOM, are negatively correlated with salinity. Terrestrial/anthropogenic inputs, riverine runoff, and mangrove porewater exchange are sources of (micro)nutrients and aromatic CDOM into the estuary. In contrast, pH, DO, TDP, SR, BIX, and tryptophan-like CDOM are positively correlated with salinity. This indicates saltwater dilution, tidal mixing, photo-oxidation, and microbial degradation processes promote the enrichment of low MW autochthonous CDOM and TDP, together with the removal of humic-like substances and other (micro)nutrients in the lower estuary. Overall, these findings have important implications for biogeochemical cycling processes driven by CDOM composition and sources in mangrove estuaries.

Eutrophication alters bacterial co‐occurrence networks and increases the importance of chromophoric dissolved organic matter composition

AbstractEutrophication affects bacterial communities by fueling them with nutrients and carbon sources. While the influence of physicochemical conditions on bacterial communities is well studied, little is known about how dissolved organic matter (DOM) quality affects bacterial interspecific interactions and community composition with increasing eutrophication. Here, we examined the relative importance of physicochemical conditions and chromophoric DOM (CDOM) composition for bacterial community variation across trophic gradients using 109 samples data collected in 33 lakes of the Yangtze‐Huaihe River basin. We found a notable increase of bacterial abundance, elevated modularity of co‐occurrence networks, and decreased habitat niche breadths from mesotrophic sites to hyper‐eutrophic sites, suggesting changes in co‐occurrence patterns with eutrophication. Variation partitioning revealed that the proportion purely explained by CDOM composition was higher at the moderate‐ and hyper‐eutrophic sites than at the mesotrophic sites. Moreover, the module structures of the networks correlated significantly with CDOM composition at the eutrophic sites but not at the mesotrophic sites. The significant negative correlation between community‐level habitat niche breadths and the intensities of the protein‐like components at the moderate‐ and hyper‐eutrophic sites indicates a strong association between biolabile protein‐like compounds and habitat specialists in nutrient and substrate enriched lake systems. Our results suggest that consideration of DOM composition can strengthen the identification of links between environmental factors and bacterial community composition and interspecific interactions, especially under resource‐rich conditions.

Absorption and Three Dimensional Fluorescence Spectra of CDOM in the Water of the Taibaishan Nature Reserve

It is very important to understand water ecology and the carbon cycle process by studying the composition, source, spectral characteristics, and influence factors of chromophoric dissolved organic matter (CDOM). The optical characteristics, composition, and source of CDOM in 71 water samples were collected from the lakes and four rivers of the Taibaishan Nature Reserve in the summer of 2019. The rivers included the Bawang, Heihe, Shitou, and Xushui Rivers. They were analyzed by UV-Vis spectral and three-dimensional fluorescence spectroscopy, combined with a parallel factor analysis model and redundant analysis. The results showed that CDOM in the water of the Taibaishan Nature Reserve contained two types of four fluorescent components, in which the humus-like components C1 and C2 were the main components of CDOM. The relative contribution of C1 and C2 to the rivers was 82%-96%, which was significantly larger than the lakes. All fluorescence indexes (FI) were larger than 1.8, the index of recent autochthonous contribution (BIX), and the index of freshness (β:α) were all approximately 0.6. The humification indexes (HIX) of the rivers were significantly larger than those of the lakes (P<0.01). The DOM in the rivers was mainly from the forest soil of the Nature Reserve, and the water quality of the lakes was affected by tourists to some extent. The results of the redundant analysis show that the CDOM spectral characteristic parameters were significantly influenced by EC for the lakes (P<0.05) and by EC, DTN, and DOC for the rivers (P<0.01).

Characteristics of the chromophoric dissolved organic matter of urban black-odor rivers using fluorescence and UV-visible spectroscopy.

Urban black-odor water (BOW) is a typical phenomenon seen in the urban water environment; it is caused by excessive pollution by organic matter and other pollutants, such as nitrogen and phosphorous. Chromophoric dissolved organic matter (CDOM) is a major optical fraction of dissolved organic matter. In this study, optical properties and components of CDOM were obtained from 178 river samples collected from five cities in China, the sample were investigated using absorption and fluorescence spectroscopy. The collected included 89 ordinary water (OW) samples, 63 mild BOW (MBOW), and 26 heavy BOW (HBOW) samples. Significant differences were found in the absorption spectra of the HBOW, MBOW, and OW samples, particularly in their optical parameters (the slope of the spectrum (S275-295), and the ratio of two absorption coefficients of CDOM (E2:E3)). Additionally, the fluorescence intensity of the humic acid-like component (F5) and soluble microbial by product-like component (F4) obtained via the fluorescence regional integration (FRI) method were 3 and 4.2 times higher in HBOW than in OW, respectively; this could be used as an indicator to distinguish OW from BOW in urban rivers. The results obtained using the redundancy method and the strong negative correlation between F4 and dissolved oxygen (DO) (r=- 0.56) suggested that the composition of CDOM could change significantly under different urban water environments (p<0.01). Different correlations were also found between F5, and a355, E2:E3, S275-295 in different BOW levels, suggesting that the optical parameters of CDOM were mainly determined by the polluted organic matter originating from terrestrial sources with large molecular humic acid-like compounds; optical parameter a355 could distinguish BOW from OW. These findings are conducive in understanding the dynamics of organic matter pollution and to discover the composition and optical properties of the CDOM in urban BOW and OW, thereby providing an effective method for tracking the spatial characteristics of BOW in urban rivers using remote sensing technologies in areas with multiple sources of pollution.

Effects of land use on the characteristics and composition of fluvial chromophoric dissolved organic matter (CDOM) in the Yiluo River watershed, China

• Effects of land use on CDOM and DOC in the Yiluo River watershed were quantified. • Atypical CDOM absorption curve exhibited a shoulder near 390 nm. • Water samples showed high tryptophan-like and humic-like fluorophores. • Crop-dominated and built-up areas had high CDOM and DOC concentrations. Chromophoric dissolved organic matter (CDOM) is a key indicator of water quality, biogeochemical state and nutrient content in freshwaters. Land use affects the concentration, quality, source, and age of CDOM in rivers. To investigate the characteristics and composition of fluvial CDOM and the effects of land use on carbon components, 37 sites were sampled during May 2017 in the Yiluo River watershed, China. In addition, water parameters, absorption and fluorescence spectral parameters of CDOM were measured in situ and in the lab. Some samples showed atypical CDOM absorption curves with an absorption shoulder at 390 nm. CDOM absorption at 440 nm [a CDOM (440)] was positively correlated with dissolved organic carbon (DOC) and fluorescence intensity (Fn). Fluorescence excitation-emission spectra indicated the presence of strong humic-like and tryptophan-like fluorophores revealing terrestrial, anthropogenic influence. Low recent autochthonous contribution index (BIX) and humification index (HIX) values indicated that autochthonous production was an important contributor to CDOM levels. Cropland-dominated subwatersheds (SWs) exhibited high a CDOM (440), Fn and DOC and forest-dominated SWs showed low CDOM concentration. At the riparian buffer scale, CDOM in the built-up-dominated areas showed the highest CDOM concentration. Moreover, built-up areas greatly influenced the concentrations of DOC and CDOM quantificationally at both the SW and riparian buffer scales; more than 64% of the overall variation in carbon components at the SW scale and 46% of DOC variation at the riparian buffer scale was explained by built-up areas. Overall, the results of our study showed that the properties of fluvial CDOM are dependent on the surrounding land use, further highlighting the importance of land use for CDOM photoreactivity in SWs and riparian buffer zones.

CDOM Optical Characteristics and Related Environmental Factors of High-turbidity Waters on the Loess Plateau

Chromophoric dissolved organic matter (CDOM) optical absorption characteristics, CDOM spectral slopes (S275-295), contribution of each component to water absorption, and the effects of environmental factors on them were analyzed to determine the sources and composition of CDOM in high-turbidity waters on the Loess Plateau. Samples in rivers and lakes (saline and freshwater) in the Loess Plateau area of Shaanxi and Inner Mongolia were collected in May 2018. The results demonstrated significant differences in CDOM absorption optical characteristics between rivers and lakes. The average aCDOM(440) (CDOM concentration, 8.45 m-1) in lakes was higher than that of rivers (2.70 m-1), and the saline lakes showed a higher CDOM concentration (13.52 m-1) than the freshwater lakes (3.38 m-1). Moreover, the light utilization efficiency of freshwater lakes is higher than that of saline lakes and turbid rivers. Great differences in pH and dissolved organic carbon (DOC) were observed between different types of water (P<0.01). The differences in electrical conductivity (EC), turbidity (Tur), and total suspended matter concentration (TSM) were significant with no statistical significances (P>0.1). The chlorophyll a concentration (Chla) in saline lakes was close to the Chla concentration in freshwater lakes if extreme values were excluded. In addition, the CDOM molecular weights of lake water were lower than those in the rivers, while CDOM molecular weights in saline lakes were lower than those in freshwater lakes based on the S275-295. Analyses of specific ultraviolet absorbance (SUVA254) were also conducted to determine the sources of CDOM in different water types, and the results showed that the more terrigenous humus were brought into the rivers and saline lakes compared with the freshwater lakes. Redundancy analysis (RDA) indicated that river and lake water quality parameters of the cumulative variance explained rates were 35.2% for river samples and 61.4% for lake samples, and 100% for samples in the saline and freshwater lakes individually. The results of RDA showed that dissolved oxygen (DO), water temperature, and EC exerted significant effects on CDOM optical properties of the river (P<0.01), while DOC, TSM, and Tur had a great influence on the CDOM optical properties of lakes (P<0.01). There was a strong correlation between pH and CDOM in the saline lakes, while DOC was significantly correlated with CDOM in the freshwater lakes (P<0.05).

Decreasing underwater ultraviolet radiation exposure strongly driven by increasing ultraviolet attenuation in lakes in eastern and southwest China

Underwater light attenuation plays an important role in modulating aquatic ecosystems and is considered a sentinel of climate change and human activity. However, knowledge of the long-term exposure of underwater ultraviolet radiation (UVR) in aquatic ecosystem is still very limited. We carried out extensive UVR measurements in different seasons in five lakes at different altitudes, collected long-term Secchi disk depth (SDD) data, developed the models between UVR diffuse attenuation coefficient (Kd) and SDD, and further assessed the long-term underwater UVR exposure. Observation results from five lakes including 259 samples showed large spatial variabilities of Kd(313) (UVB) from 0.83 to 5.91 m−1 and Kd(340) (UVA) from 0.51 to 4.67 m−1. Chromophoric dissolved organic matter (CDOM) absorption coefficients were significantly correlated with Kd(313) and Kd(340). Thus, the effects of climate change and human activity on CDOM abundance, source and composition may significantly alter UVR attenuation in aquatic environments. The long-term underwater UVR exposure, which was estimated from significant positive correlations between 1/SDD and Kd(313) and Kd(340), and incident UVR, significantly decreased in Lake Fuxianhu, Lake Erhai, and Lake Qiandaohu. The regime shift from clear water state to turbid state in Lake Erhai around 2001–2003 dramatically decreased underwater UVR exposure. In conclusion, increasing UVR attenuation played a more important role in determining underwater UVR exposure than decreasing incident UVR with the relative contributions of 89.9% and 87.7% in Lake Fuxianhu, 98.0% and 97.7% in Lake Erhai, 94.4% and 92.5% in Lake Qiandaohu for UVB and UVA exposure, respectively. This is the first study to elucidate the long-term trend of underwater UVR exposure considering both increasing UVR attenuation and decreasing incident UVR.

Characterization of DOC and CDOM and their relationship in turbid waters of a high-altitude area on the western Loess Plateau, China.

Dissolved organic carbon (DOC) and chromophoric dissolved organic matter (CDOM) in rivers and reservoirs on the western Loess Plateau, which is an area of severe soil erosion, were investigated in September 2017 to analyze the CDOM characteristics and composition, DOC distribution and influence of environmental factors on these parameters. Great differences of water parameters were exhibited between different groups based on the analysis of variance (p < 0.01). The results indicated that rivers exhibited higher DOC concentrations (mean: 3.70 mg/L) than reservoir waters (mean: 2.04 mg/L). Artificial and agricultural lands exert a large influence on DOC concentrations, which verifies the hypothesis that intense anthropogenic activity results in high DOC concentrations. The CDOM absorption at 350 nm [aCDOM(350)] of tributary water samples was 2.73 m-1, which was higher than that in the Yellow River (1.71 m-1) and reservoir waters (1.33 m-1). The effects of DOC, TC and turbulence (Tur) on CDOM are positive and significant (p < 0.05) according to the multiple linear regressions. An analysis of the optical characteristics of CDOM indicated that waters on the Loess Plateau contained abundant humic acid and higher levels of allochthonous DOM with a higher molecular weight (MW) based on the spectral slopes (S) and specific UV absorbance (SUVA254) values.

Characteristics of Absorption Spectra of Chromophoric Dissolved Organic Matter in the Pearl River Estuary in Spring

In this study, absorption variation of chromophoric dissolved organic matter (CDOM) was investigated based on spectroscopic measurements of the water surface and bottom during a cruise survey on 2–12 May 2014 in the Pearl River Estuary (PRE). Multiple spectral signatures were utilized, including the absorption ratios E2/E3 (a(250)/a(365)) and E2/E4 (a(254)/a(436))) as well as the spectral slopes over multiple wavelength ranges. The horizontal variations of a(300), E2/E3, spectral slope (S) of Ultraviolet C (SUVC, 250–280 nm), Ultraviolet B (SUVB, 280–315 nm), and S275–295 (275–295 nm) were highly correlated, revealing that CDOM of terrigenous origin in the upper estuary contained chromophores of larger molecular size and weight, while the marine CDOM in the lower estuary comprised organic compounds of smaller molecular size and weight; the molecular size of surface CDOM was generally larger than that at the bottom. Results of Gaussian decomposition methods showed that CDOM in the middle estuary of terrigenous origin produced more Gaussian components per spectrum than those of marine origin in the lower estuary and the adjacent Hong Kong waters. The surface CDOM composition was more diverse than at the bottom, inferred by the finding that the average number of Gaussian components yielded per surface sample (5.44) was more than that of the bottom sample (4.8). A majority of components was centered below 350 nm, indicating that organic compounds with relatively simple structures are ubiquitous in the estuary. Components centered above 350 nm only showed high peaks at the head of the estuary, suggesting that terrigenous CDOM with chromophores in complex structures rapidly lose visible light absorptivity during its transport in the PRE. The relatively low and homogenous peak heights of the components in Hong Kong waters imply higher light stability and composition consistency of the marine CDOM compared with the terrigenous CDOM.

Dissolved carbon and CDOM in lake ice and underlying waters along a salinity gradient in shallow lakes of Northeast China

The variations of DOC and DIC concentrations in lake ice and underlying waters were examined in 40 shallow lakes across the Songnen Plain, Northeast China. The lakes, frozen annually during winter, included freshwater and brackish systems (EC > 1000 μS cm−1; range: 171–12607 μS cm−1 in underlying water). Results showed that lake ice contained lower DOC (7.2 mg L−1) and DIC (6.7 mg L−1) concentration compared to the underlying waters (58.2 and 142.4 mg L−1, respectively). Large differences in DOC and DIC concentrations of underlying waters were also observed between freshwater (mean ± SD: 22.3 ± 11.5 mg L−1, 50.7 ± 20.6 mg L−1) and brackish lakes (83.3 ± 138.0 mg L−1, 247.0 ± 410.5 mg L−1). A mass balance model was developed to describe the relative distribution of solutes and chemical attributes between ice and the underlying waters. Results showed that water depth and ice thickness were the key factors regulating the spatial distribution of solutes in the frozen lakes. Chromophoric dissolved organic matter (CDOM) absorption coefficient at 320 nm, aCDOM(320) and specific UV absorbance (SUVA254) were used to characterize CDOM composition and quality. Compared to the underlying waters, CDOM present in ice largely included low aromaticity organic substances, an outcome perhaps facilitated by ice formation and photo-degradation. In ice and underlying freshwaters, CDOM predominantly included organic C fractions of high aromaticity, while low aromaticity organic substances were observed for brackish lakes. Results of this study suggest that, if water salinity increases due to climate change and anthropogenic activities, significant changes can occur in the dissolved carbon and fate of CDOM in these shallow lakes.

Response of chromophoric dissolved organic matter dynamics to tidal oscillations and anthropogenic disturbances in a large subtropical estuary

Estuaries support the livelihood of ~75% of the world's population and maintain high primary production in coastal waters, which are often subjected to strong tides and anthropogenic disturbances. There is a paucity of information on how the optical composition and bioavailability of chromophoric dissolved organic matter (CDOM) are influenced by tidal oscillations in estuaries with highly urbanized surrounding areas. We examined the semi-diurnal Qiantang Bore, one of the Earth's three most predominant tide bores, and found that dissolved organic carbon (DOC), CDOM absorption a(254) and terrestrial humic-like C1, tryptophan-like C2 and C5, fulvic-like C3, and microbial humic-like C4 decreased markedly with increasing salinity. This suggests that physical mixing of riverine freshwater and saltwater can shape the optical composition of CDOM in the estuary. This was supported by the semi-diurnally and hourly observations at Zhijiang (salinity ~0.1‰, upstream of the estuary) that DOC, bioavailable DOC (BDOC), C1–C2, and C4–C5 increased markedly with decreasing tidal level, while DOC and C1–C5 increased notably with increasing salinity. We further found δ18O was enriched with increasing tidal level, while tryptophan-like C2 and C5, and fulvic-like C3 decreased significantly with increasing tidal level at Zhapu (salinity ~7‰, downstream of the estuary). Furthermore, DOC, BDOC, C1, and C4 decreased, while δ18O and C3 increased markedly with increasing salinity. Further evidences come from the notably lower mean first principal component (PC1) scores at Zhijiang and Zhapu, both positively associated with anthropogenic tryptophan-like inputs, were observed during ebb than during flood tides, and PC1 at Zhijiang increased notably with increasing salinity. We conclude that anthropogenic inputs contributed primarily to the CDOM pool in the estuary and are mediated by the physical mixing of riverine freshwater and seawater, and ebb tides are often associated with enhanced anthropogenic CDOM with relatively high bioavailability.

Response of Chromophoric Dissolved Organic Matter Composition to Different Hydrological Scenarios in Large Eutrophic Lake Taihu

Chromophoric dissolved organic matter (CDOM) is a fraction of dissolved organic matter that can strongly absorb light in the ultraviolet and blue regions and plays an important role in the biogeochemical cycling of carbon, nitrogen, and phosphorus. Unraveling the sources, optical composition, and corresponding spatial variabilities of CDOM can improve our understanding of carbon, nitrogen, and phosphorus cycling in lakes and lake water quality management. CDOM spectral absorption and fluorescent excitation-emission matrices were measured to investigate the compositional dynamics of CDOM under different hydrological scenarios. Our results showed that the mean value of dissolved organic carbon (DOC) concentration of (8.11±1.26) mg·L-1 in the rainy season was significantly higher than that in the dry season (3.53±1.19) mg·L-1 (t-test, P<0.01), whereas the mean spectral slope S275-295 of (20.89±1.90) μm-1 in the dry season was significantly greater than that in the rainy season (19.09±1.81) μm-1 (t-test, P<0.001). Three fluorescent components were identified using parallel factor analysis, and we further found that the dynamics of the three CDOM components were strongly influenced by hydrological conditions. Fluorescence intensity (Fmax) of the terrestrial humic-rich component C2 increased with increasing water levels and rainfall. Significant negative relationships were found between all three fluorescent components and dissolved oxygen (P<0.01), suggesting that all three components served as important substrates for microbial processing. Significant positive relationships were found between the terrestrial humic-rich C2 and tryptophan-like C1 and chlorophyll-a and chemical oxygen demand, indicating that anthropogenic inputs and algal degradation contributed significantly to the CDOM pool in Lake Taihu. We further found a significant positive relationship between DOC concentration and Fmax of terrestrial humic-rich C2 (r2=0.58, P<0.001), suggesting that DOC in Lake Taihu was primarily derived from allochthonous input.

Implications of irradiance exposure and non-photochemical quenching for multi-wavelength (bbe FluoroProbe) fluorometry

Multi-wavelength fluorometers, such as the bbe FluoroProbe (FP), measure excitation spectra of chlorophyll a (Chl-a) fluorescence to infer the abundance and composition of phytoplankton communities as well as the concentration of chromophoric dissolved organic matter (CDOM). Experiments were conducted on laboratory cultures and on natural communities of freshwater phytoplankton to determine how the response of phytoplankton to high irradiance might affect fluorometric estimates of community composition and concentrations of Chl-a and CDOM. Cultures of a representative cyanobacterium, bacillariophyte, synurophyte, cryptophyte, and chlorophyte revealed changes in Chl-a excitation spectra as irradiance was increased to saturating levels and non-photochemical quenching (NPQ) increased. The degree of change and resulting classification error varied among taxa, being strong for the synurophyte and cryptophyte but minimal for the cyanobacterium. Acute-exposure experiments on phytoplankton communities of varying taxonomic composition from five lakes yielded variable results on apparent community composition. There was a consistent decrease in CDOM estimates, whereas Chl-a estimates were generally increased. Subsequent exposure to low PAR relaxed NPQ and tended to reverse the effects of high irradiance on composition, total Chl-a, and CDOM estimates. Relaxation experiments on near-surface communities in a sixth, large lake, Georgian Bay, showed that total Chl-a estimates increased by 44% on average when dark treatments were used to relax NPQ, though, in contrast to the findings from the small lakes, there was little effect on CDOM estimates. We observed a statistically-significant, negative linear relationship between the photon flux density of in situ irradiance and the accuracy of taxonomic assignment by FP in Georgian Bay. Not discounting the correlations between light intensity and the accuracy of the FP that were observed in this study, we conclude that the applicability of the reference spectra to the system under investigation is a more important consideration than variability in natural irradiance conditions.