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A Systematic Examination of the Relationships Between CDOM and DOC in Inland Waters in China

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A Systematic Examination of the Relationships Between CDOM and DOC in Inland Waters in China Hydrol. Earth Syst. Sci., 21, 5127–5141, 2017 https://doi.org/10.5194/hess-21-5127-2017 © Author(s) 2017. This work is distributed under the Creative Commons Attribution 3.0 License. A systematic examination of the relationships between CDOM and DOC in inland waters in China Kaishan Song1, Ying Zhao1,2, Zhidan Wen1, Chong Fang1,2, and Yingxin Shang1 1Northeast Institute of Geography and Agroecology, CAS, Changchun, 130102, China 2College of Resources and Environment, University of Chinese Academy of Sciences, Beijing, 100049, China Correspondence to: Kaishan Song ([email protected]) Received: 25 March 2017 – Discussion started: 4 April 2017 Revised: 6 September 2017 – Accepted: 6 September 2017 – Published: 11 October 2017 Abstract. Chromophoric dissolved organic matter (CDOM) 1 Introduction plays a vital role in the biogeochemical cycle in aquatic ecosystems. The relationship between CDOM and dissolved Inland waters play a disproportionate role in global carbon organic carbon (DOC) has been investigated, and this signif- cycling with respect to carbon transportation, transformation, icant relationship lays the foundation for the estimation of and carbon storage (Tranvik et al., 2009; Raymond et al., DOC using remotely sensed imagery data. The current study 2013; Verpoorter et al., 2014; Yang et al., 2015). However, examined samples from freshwater lakes, saline lakes, rivers the amount of dissolved organic carbon (DOC) stored in and streams, urban water bodies, and ice-covered lakes in the inland waters is still unclear or the uncertainty is still China for tracking the variation of the relationships between needed to be evaluated (Tranvik et al., 2009). Determina- DOC and CDOM. The regression model slopes for DOC vs. tion of DOC concentration is straightforward through field aCDOM (275) ranged from extremely low 0.33 (highly saline sampling and laboratory analysis (Findlay and Sinsabaugh, lakes) to 1.03 (urban waters) and 3.01 (river waters). The low 2003). However, there are millions of lakes in the world, and values were observed in saline lake waters and waters from many of them are remote and inaccessible, making it im- semi-arid or arid regions, where strong photobleaching is ex- possible to evaluate DOC concentrations using routine ap- pected due to less cloud cover, longer water residence time, proachs (Cardille et al., 2013; Brezonik et al., 2015; Pekel and daylight hours. In contrast, high values were found in et al., 2016). Researchers have found that remote sensing waters developed in wetlands or forest in Northeast China, might provide a promising tool for quantification of DOC where more organic matter was transported from catchment in inland waters on a large scale through linking DOC with to waters. The study also demonstrated that closer relation- chromophoric dissolved organic matter (CDOM), particu- ships between CDOM and DOC were revealed when aCDOM larly for inland waters situated in remote areas with little ac- (275) were sorted by the ratio of aCDOM.250/=aCDOM (365), cessibility (Tranvik et al., 2009; Kutser et al., 2015; Brezonik which is a measure for the CDOM absorption with respect et al., 2015). to its composition, and the determination of coefficient of As one of the optically active constituents in waters, the regression models ranged from 0.79 to 0.98 for different CDOM can be estimated through remotely sensed signals groups of waters. Our results indicate the relationships be- (Yu et al., 2010; Kutser et al., 2015), and acts as a proxy tween CDOM and DOC are variable for different inland wa- in many regions for the amount of DOC in the water col- ters; thus, models for DOC estimation through linking with umn. As shown in Fig. 1, CDOM and DOC in the aquatic CDOM absorption need to be tailored according to water ecosystems are mainly originated from natural external (al- types. lochthonous) and internal (autochthonous) sources, in addi- tion to direct discharge from anthropogenic activities (Zhou et al., 2016). Generally, the autochthonous CDOM essen- tially originates from algae and macrophytes, and mainly consists of various compounds of low molecular weights Published by Copernicus Publications on behalf of the European Geosciences Union. 5128 K. Song et al.: CDOM versus DOC for inland waters (Findlay and Sinsabaugh, 2003; Zhang et al., 2010). The al- ined (Gonnelli et al., 2013). In addition, the SUVA254 and lochthonous CDOM is mainly derived from the surrounding M value may be used to classify CDOM into different groups terrestrial ecosystems, and it comprises a continuum of small and enhance the relationship with DOC based on CDOM ab- organic molecules to highly polymeric humic substances. In sorption grouping. terms of CDOM originating from anthropogenic sources, it Some studies have investigated the spatial and seasonal contains fatty acids, amino acids, and sugar; thus, the com- variations in CDOM and DOC in ice-free season in lakes, position of CDOM is more complex than that from natural rivers, and oceans (Vodacek et al., 1997; Neff et al., 2006; systems (Zhou et al., 2016; Zhao et al., 2016a). Hydrolog- Stedmon et al., 2011; Brezonik et al., 2015), but less is ical factors also affect the DOC and CDOM characteristics known about saline lakes (Song et al., 2013; Wen et al., and particularly the discharge, catchment area, land use, and 2016). Even less is known about urban waters influenced by travel time are the important ones (Neff et al., 2006; Jaffé et sewage effluent and waters with ice cover in winter (Belzile al., 2008; Spencer et al., 2012). et al., 2002; Zhao et al., 2016b). A significant relationship CDOM is a light-absorbing constituent, which is par- between CDOM and DOC was observed in the Gulf of Mex- tially responsible for the color in waters (Bricaud et al., ico, and a stable regression model was established between 1981; Reche et al., 1999; Babin et al., 2003). The chem- DOC and aCDOM (275) and aCDOM (295) (Fichot and Ben- ical structure and origin of CDOM can be character- ner, 2011). Similar results were also found in other estuaries ized by its absorption coefficients (aCDOM(λ)) and spec- along a salinity gradient, for example the Baltic Sea surface tral slopes (De Haan and De Boer, 1987; Helms et al., water (Kowalczuk et al., 2010) and the Chesapeake Bay (Le 2008). Weishaar et al. (2003) has proven that the carbon et al., 2013). However, Chen et al. (2004) found that the rela- specific absorption coefficient at 254 nm, e.g., SUVA254 is tionship between CDOM and DOC was not conservative due a good tracer for the aromaticity of humic acid in CDOM, to estuarine mixing or photodegradation. Similar arguments while the ratio of CDOM absorption at 250 to 365 nm, were raised for the Congo River and waters across main- i.e., aCDOM .250/=aCDOM .365/ herein M value, has been land USA (Spencer et al., 2009, 2012). In addition, seasonal successfully used to track the variation in DOM molecu- variations were observed in some studies due to the mixing lar weight (De Haan and De Boer, 1987). Biodegradation of various end-members of CDOM from different terrestrial and photodegradation are the major processes to determine ecosystems and internal sources (Zhang et al., 2010; Spencer the transformation and composition of CDOM (Findlay and et al., 2012; Yu et al., 2016; Zhou et al., 2016). Sinsabaugh, 2003; Zhang et al., 2010), which ultimately af- As demonstrated in Fig. 1, several factors influence the as- fect the relationship between DOC and CDOM (Spencer sociation between DOC and CDOM; thus, the relationship et al., 2012; Yu et al., 2016). With prolonged sunlight radi- between DOC and CDOM may vary with respect to their ation, some of the colored fraction of CDOM is lost by the origins, photo- or bio-degradations (Williamson and Rose, photobleaching processes (Miller et al., 1995; Zhang et al., 2010), and hydrological features, which is worth systematic 2010), which can be measured by the light absorbance de- examination. In this study, the characteristics of DOC and creasing at some specific (diagnostic) wavelength, e.g., 250, CDOM in different inland waters across China were exam- 254, 275, 295, 360, and 440 nm. ined to determine the spatial features associated with land- It should be noted that aCDOM (440) is usually used by scape variations, hydrologic conditions and saline gradients. the remote sensing community due to this wavelength be- The objectives of this study are to (1) examine the relation- ing overlapped with pigment absorption at 443 nm; thus, re- ship between CDOM and DOC concentrations across a wide porting aCDOM (440) has the potential to improve chloro- range of waters with various physical, chemical, and biolog- phyll a estimation accuracy (Lee et al., 2002). The relation- ical conditions, and (2) develop a model for the relationship ship between CDOM and DOC varies since CDOM loses between DOC and CDOM based on the sorted CDOM ab- color, while the variation of DOC concentration is almost sorption feature, e.g., the M values, and aiming to improve negligible. Saline or brackish lakes in the arid or semi-arid the regression modeling accuracy. regions are generally exposed to longer sunlight radiation; thus, CDOM absorbance decreases, while DOC is accumu- lated due to the longer residence time (Curtis and Adams, 2 Materials and methods 1995; Song et al., 2013; Wen et al., 2016). Compared to pho- todegradation of CDOM, the biodegradation processes by The dataset is composed of five subsets of samples col- microbes are much more complicated, and extracellular en- lected from various types of waters across China (Table 1; zymes are the key factors required to decompose the high- Fig. 2), which encompassed a wide range of DOC and molecular-weight CDOM into low-molecular-weight sub- CDOM concentrations.
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