1. Introduction
Natural aquatic ecosystems such as marine and freshwater ecosystems are crucial for
maintaining the general balance of the environment (Band et al., 2012). Human population is the main beneficiary of these aquatic ecosystems as they provide
clean water for drinking and irrigation, habitats for fisheries, maintenance of biogeochemical
cycles. Watersheds or drainage basins contain these aquatic ecosystems, which are
directly responsible for nutrient cycling, carbon storage (Allan, 1995), soil formation, wildlife corridor (Clipp and Anderson, 2014) sediment filtration, flood and erosion control.
In a simple explanation, a watershed is a land area that drains into a water body.
This can be a river, lake, or stream, and the watershed can be small in size with
a single waterway or very large, comprising one or more streams and a main water body.
Watersheds extensively affect surface water quality. The land area of the watershed
is connected through the movement of water, and collectively, all the chemical, physical,
and biological processes occurring in the area are responsible for the functionality
of the ecosystems. The rapid growth of the human population and the increasing rate
of urbanization negatively affect watershed maintenance and health. In particular,
the degradation of water quality has been a key focus for decades (Bolan et al., 2011; Chen et al., 2015; Chen et al., 2007; Grimm et al., 2008). Human activities such as urban development, agriculture, and animal husbandry are
strongly reflected in water quality parameters, such as total nitrogen (TN) and total
phosphorus (TP) concentration (Chen et al., 2007). Dissolved organic matter (DOM) has shown a tendency to reflect water quality because
it is closely related to the basic water quality parameters of a water body, such
as biological oxygen demand (BOD) and chemical oxygen demand (COD) (Lee et al., 2020). The type and abundance of DOM provide valuable information concerning human impacts
on aquatic ecosystems (Clayton et al., 2017). For example, an obscene proportion of protein-like organic matter or the presence
of microbial humic-like substances in DOM within the ecosystem is associated with
the presence of anthropogenic activities and is utilized as an indicator to assess
human impact on water pollution (Clayton et al., 2017; Petrone et al., 2011; Tanaka et al., 2014).
The composition of DOM can also be considerably altered by effluents from wastewater
treatment plants (Zhu et al., 2020) and/or by unintentional residential wastewater discharge (Kim et al., 2012). The efficiency of the wastewater treatment process can be assessed by investigating
the change in the DOM composition of downstream water (Meng et al., 2013; Stolpe et
al., 2014). DOM has been commonly used as an indicator of the land use of watersheds
and a predictor of pollution sources in surface water bodies (Derrien et al., 2019; Lozovik et al., 2007; Retelletti Brogi et al., 2018). The spectral fingerprint of humic substances (HS) generated from agricultural land
use and forest watersheds has been distinguished by DOM analyses (Graeber et al., 2012). The DOM in a watershed is affected in multiple ways by human disturbances, which
can be verified because in situ-produced DOM shows unique signals and differences in its spectroscopic indices from
terrestrially derived DOM (Stanley et al., 2012).
DOM characterization mainly employs a three-dimensional fluorescence spectrum (3D-EEM)
along with ultraviolet-visible spectroscopy (Arguelho et al., 2017; Li, Lu et al., 2021). Only a certain fraction of DOM absorbs light and produces a signal, and even a
minor fraction fluoresces (Gilchrist and Reynolds, 2014). However, optical measurements of these DOM sub-fractions have provided useful insights
into DOM composition, which has been used extensively in recent years as a reliable
parameter (DeVilbiss et al., 2016; Kamjunke et al., 2017; Li, Zhang et al., 2022). There is a range of technical methods besides spectroscopy, such as isotope analysis
(Guo et al., 2009) and chromatographic methods (high-performance liquid chromatography (HPLC)-size
exclusion chromatography (SEC)) (Her et al., 2003). However, spectroscopic methods are prevalent owing to the many conveniences of
these complex methodologies and their comparatively high sensitivity, ease of use,
fast responses, and low-cost instrumentation and processing (Conmy et al., 2014; Li and Hur, 2017).
The inherent chemical complexity and heterogeneity of DOM make it necessary to resolve
the overlapped fluorescence signals and to remove other spectral interferences from
the samples during fluorescence spectroscopic analysis (Gilchrist and Reynolds, 2014). This makes the fluorescence excitation-emission matrix (FEEM) itself low in accuracy
and reliability for directly identifying the source or composition of the DOM (Ma and Li, 2020). This hurdle was overcome by using mathematical techniques, specifically decomposition
methods and multivariate analyses. The most commonly utilized tool in watershed studies
is parallel factor analysis (PARAFAC), in which the 3D-EEM is separated into individual
components (Gu et al., 2020). Combining fluorescence spectroscopy with mathematical tools such as PARAFAC has
heightened its application potential (Bro, 1997; Stedmon and Bro, 2008; Stedmon et al., 2003). Built-in programming tools such as the DOMFluor open toolbox in MATLAB software
and staRdom package in R programming make PARAFAC more convenient to use for research
purposes and it has been extensively utilized in the majority of the watershed studies
(DeVilbiss et al., 2016; Lee et al., 2020; Li, Zhang et al., 2022; Stanley et al., 2012).
In order to understand DOM optical property measurements in depth, it is necessary
to consider the environmental context and the diversity of production, transformation,
transport, and storage mechanisms involved in the process (D’Andrilli et al., 2022). Because the applicable ecosystems are versatile, the range of available literature
in the field is also plentiful. This review aims to gain a general understanding of
the use of DOM fluorescence analysis in watershed studies, focusing on recent years
and how the field of watershed studies has utilized DOM fluorescence to improve existing
knowledge and techniques.
Fig. 1. Schematic diagram of the utilization of FDOM characterization with Fluorescence Excitation Emission Matrices (FEEM) and statistical analysis for diagnosis and source identification of watershed pollution.
2. Separation of Independent DOM fluorescent Components
The different fluorescent components present in DOM samples can be differentiated
by the distinct wavelengths of each peak separated in the PARAFAC. Moreover, source
determination can be performed based on the specificity of these components (Murphy et al., 2014). The peak representation of the relevant DOM components provides a better understanding
of the collected data. However, it is notable that the peak positions can shift with
changes in the ionic strength, pH, and other solvent properties (Osburn et al., 2014). Owing to the diverse uses of the FEEM approach in DOM studies, PARAFAC models have
now been applied to natural systems such as freshwater, marine, and soil-derived waters
alongside engineered systems (D’Andrilli et al., 2022; Ishii and Boyer, 2012; Stedmon et al., 2003; Wu et al., 2022).
There are commonly occurring PARAFAC components that are defined by a range of excitation
and emission wavelengths across a range of studies (Ishii and Boyer, 2012). The most commonly occurring fluorescent dissolved organic matter (FDOM) can be
categorized as either humic-like type or protein-like type (Stedmon and Cory, 2014). Humic-like components are very versatile. They show a wide range of excitation
and emission wavelengths, as well as different chemical qualities mainly related to
their natural origin. Researchers have observed the three most commonly occurring
humic-like components in both natural and engineered systems. The first component
has an excitation peak at approximately 260 nm or less with a broad emission band
centered at 400–500 nm (Ishii and Boyer, 2012). This component is most commonly abundant in DOM dominated by terrestrial precursor
material from soil extractions, soil solutions, forested streams, wetlands, and tree
leaves, especially during warm months in spring and summer (Ohno and Bro, 2006; Stedmon and Markager, 2005; Stedmon et al., 2003). This peak position is classified as humic-like peak A in the Coble peak nomenclature
(1996) (Coble, 2007; Coble et al., 1998).
The second humic-like component consists of a primary excitation peak wavelength of
approximately 260 nm or less, with a broad emission band centered at 400–500 nm. It
is similar to the first humic-like component; however, this second component also
has a secondary excitation peak at 340–420 nm (Ishii and Boyer, 2012). The secondary peak is labeled as peak C (humic-like peak C) in the Coble peak nomenclature
(Murphy et al., 2014). In a natural environment, peaks C and A are always observed together, but their
ratio exhibits some variability. This humic-like component has been identified in
DOM from a wide variety of aquatic systems, including those dominated by terrestrial
and potential secondary sources of microbial input (Lapierre and Frenette, 2009; Stedmon and Markager, 2005).
Another fluorescent component, the microbial humic-like component, has a primary and
secondary excitation peak, occurring at 260 nm or less and 295–380 nm, respectively
secondary excitation peak at 295–380 nm and a single emission peak at 374–450 nm.
Studies have suggested that microbial humic-like fluorophores are similar to those
of terrestrial and marine precursors, which are traditionally classified as humic-like
peaks A and M, where peak M implies a marine humic-like component (Coble et al., 1998; Ishii and Boyer, 2012). Peak M was originally derived from bloom conditions in the Gulf of Maine (Coble, 1996) and the Arabian Sea (Coble et al., 1998). The M peak of microbial humic-like components has also been observed in non-marine
environments (Stedmon and Markager, 2005) and has been found associated with recent microbial activity, rather than arising
exclusively from a marine source. These are a family of humic-like compounds that
share a common fluorophore backbone with a different ring substitution, which can
fluoresce at slightly different excitation and emission maxima (Coble et al., 2014). Therefore, within any given sample, the position of the humic-like peak provides
reliable information regarding chromophoric dissolved organic matter (CDOM) composition,
organic matter source, and environmental conditions (D’Andrilli et al., 2022; Ishii and Boyer, 2012).
The peak positions for protein-like components are much less variable than those for
humic-like components (Ishii and Boyer, 2012). These peaks were found to be more readily resemble the pure compounds and unlikely
to be influenced by the environment or source (Coble et al., 1998; Ishii and Boyer, 2012). These amino acid-like peaks are similar to tyrosine and tryptophan, presenting
their respective positions in FEEM for tyrosine and tryptophan at an excitation/emission
of 230, 275/305 nm and 230, 275/340 nm, respectively. Protein-like fluorescence in
natural waters tends to arise from a combination of free and combined amino acids
rather than pure compounds. This is reflected in the PARAFAC output, which has a border
range of emission maxima for tyrosine and tryptophan-like component separation (peaks
B and T in the Coble peak nomenclature) (Coble, 1996; Coble et al., 2014). The fluorescence emission maximum for proteins also depends on the hydrophobicity
of the molecular sites surrounding the amino acid moiety(D’Andrilli et al., 2022; Stedmon and Cory, 2014).
Multiplex fluorescence peaks have been observed in areas of active biological productivity,
other than the protein-like (amino acid-like) peaks. These include chlorophyll-like
pigment peaks, quinone-like peaks, (Cory and McKnight, 2005) as well as several unidentified compounds such as fluorophore N (Coble, 1996) and many more newly found unspecified components (e.g., Component 9 in Murphy et
al., 2009). The earliest peak nomenclature defined by Coble et al. (1990) (Coble, 1996; Coble et al., 1990, 1998) and Stedmon et al. (2003) (Stedmon et al., 2003) has been the most widely used, and the peak distinction is clear. The common labels
for the identified regions of the observed fluorescence peaks with excitation-emission
wavelengths of aquatic DOM are summarized in Table 1.
Table 1. Labels for identified regions of commonly observed fluorescence peaks in an excitation-emission spectrum of aquatic DOM
Peak label
|
Excitation maximum (nm)
|
Emission maximum (nm)
|
Description of fluorophores
|
B
|
275
|
305
|
Tyrosine-like, protein-likea |
T
|
275
|
340
|
Tryptophan-like, protein-likea |
A
|
260
|
400-460
|
Humic-likea |
M
|
290-310
|
370-410
|
Marine humic-likea |
C
|
320-360
|
420-460
|
Humic-likea |
D
|
390-455
|
509-512
|
Soil fulvic acidb |
a: Coble, 2007; b: Stedmon et al., 2003 Note: Peak M has subsequently been observed in nonmarine environments.
|
3. Fluorescence and Spectral Indices
The DOM composition and sources in watersheds are often correlated with fluorescence
indices calculated from 3D-EEM data. These indices can simply be defined as the ratio
of the fluorescence intensity measured at two different regions in the optical space
that should be chemically reasonable (Gabor et al., 2014). For decades, researchers have developed these fluorescence indices concurrent with
their studies (Chen et al., 1977; Weishaar et al., 2003; Zsolnay et al., 1999). Hence, the fluorescence indices were targeted to address system-specific questions,
such as the identification of soil organic matter in groundwater (Kalbitz et al., 2000), predicting the inactivation of bacteria during ozonation in the wastewater treatment
process, (Wu et al., 2018) and many more source-detection and pollution-detection applications throughout the
years (Chaves et al., 2020; Li, Zhao et al., 2022; Shi et al., 2022; Zhang et al., 2021).
More recently, researchers have been able to develop fluorescence indices on a system-specific
scale, where they can be applied in a wide range of systems (Gabor et al., 2014). The humic-like peak in NOM is mostly the key focus in developing fluorescence indices,
but the intensities associated with humic-like and protein-like peaks have also been
extensively studied (Kalbitz et al., 2000; Ohno and Bro, 2006; Zsolnay et al., 1999). The general interpretations of fluorescence indices are most likely to vary with
solution properties, such as salinity, pH, and organic matter source (Gabor et al., 2014). The commonly used fluorescence indices for freshwater systems are described along
with their relative wavelength ratios and references in Table 2.
Table 2. Fluorescence indices for freshwater systems with their relative wavelength ratios and references.
Fluorescence Indices
|
Parameters
|
Comments
|
Reference
|
Humification Index (HIXEM)
|
The area under the em spectra at 435–480 nm divided by the peak area at 300–345 nm + 435–480
nm, at ex of 254 nm
|
Indicator of humic substance or extent of humification. Higher values indicate an
increasing degree of humification
|
(Ohno and Bro, 2006; Zsolnay et al., 1999)
|
Freshness Index (β/α) (BIX)
|
The ratio of em intensity at 380 nm divided by the maximum em intensity between 420
nm and 435 nm at ex of 310 nm
|
β peak: recently created (likely microbial) organic matter α peak: older, more decomposed organic matter. β/α : Indicates the proportion of recently produced DOM. Developed for and mostly used in estuarine environments.
|
(Huguet et al., 2009; Parlanti et al., 2000; Wilson and Xenopoulos, 2008)
|
Fluorescence Index (FI)
|
The ratio of em wavelengths at 470 nm and 520 nm, obtained at ex of 370 nm
|
Indicates if precursor material for DOM is more microbial (FI~1.8) in nature or more
terrestrially derived (FI~1.2).
|
(Cory et al., 2010; Cory and McKnight, 2005; McKnight et al., 2001)
|
Peak T/Peak C ratio
|
The ratio of maximum fluorescence at ex 275 nm/em 350 nm (Peak T) to max intensity of the region at ex 320–340 nm/ em 410–430 nm (Peak C).
|
Used to identify the impact of sewage effluent on a river. Indicates biochemical oxygen demand relative to dissolved organic carbon (BOD/DOC)
|
(Baker, 2001)
|
Note: em = emission wavelengths, ex = excitation wavelengths
|
Alongside fluorescence spectroscopy, UV-Vis spectroscopic studies have also prominently
utilized spectral parameters to analyze CDOM. UV-Vis absorption spectra have a rather
low sensitivity compared to fluorescence spectra, and the gathered information is
insufficient to conclude only from the UV-Vis spectra (Li and Hur, 2017). However, these spectra are still widely used as common and easy measurement methods
to estimate CDOM abundance, reactivity, quality, and source tracking. Researchers
have previously used UV spectral parameters in a site-specific manner. For examples,
natural system studies mostly applied the results of absorption coefficients and spectral
slope parameters, whereas engineered systems more frequently used absorbance and differential
absorbance spectra (Li and Hur, 2017; Peacock et al., 2014). Similar to fluorescence indices, spectral indices require generalization for applicability.
The most commonly observed UV indices in watershed studies are listed in Table 3.
Table 3. Most commonly observed UV indices in freshwater-related watershed studies.
Absorbance index
|
Calculation
|
Purpose
|
Reference
|
A254, A280, A300 |
Absorption value (arbitrary units) of the given excitation wavelength in nm
|
Absorptivity at 254 nm that is very readily absorbed by organic matter in the water.
UV254 parameter to other water quality parameters that provide a measure of organic matter
in the water. Absorptivity at 300 nm and 280 nm strongly correlated with the aromatic carbon content
for seven aquatic fulvic acids
|
(Edzwald et al., 1985; Lawrence, 1980; Mcknight et al., 1997)
|
Specific ultraviolet absorbance at 254 nm [SUVA254 (L mg-C−1 m−1)]
|
Absorption coefficient at 254 nm divided by DOC concentration
|
Absorbance per unit carbon. Typically, a higher number is associated with greater
aromatic content
|
(Weishaar et al., 2003)
|
Spectral slopes (S275–295, S290–350, S350–400)] (nm−1)
|
Nonlinear fit of an exponential function to the absorption spectrum over the wavelength
range
|
Higher S values indicate low molecular weight material and/or decreasing aromaticity
|
(del Vecchio and Blough, 2002; Helms et al., 2008)
|
Spectral slope ratio (SR) S275–295 (nm−1): S350–400 (nm−1)
|
Spectral slope S275–295 divided by spectral slope S350–400 |
Negatively correlated to DOM molecular weight and a general increase in CDOM
|
(Helms et al., 2008)
|
Note: em = emission wavelengths, ex = excitation wavelengths
|
4. Applications of DOM Fluorescence for Watershed Studies
The watershed mostly consists of a large land area and a related water body. In such
cases, point sampling can be inconvenient and overconsume resources. Therefore, a
strategy for developing easy and alternative methods should be considered, where the
research area of watershed pollution source tracking is mostly associated with DOM
fluorescence studies (Li and Hur, 2017). DOM analytical tools in watershed studies have attracted the attention of the water
research community for more than 20 years, and such high attractiveness has led to
the publication of several related review articles (Andrade-Eiroa et al., 2013; D’Andrilli et al., 2022; Ishii and Boyer, 2012; Stedmon and Bro, 2008; Stedmon et al., 2003).
It is important to study how DOM fluorescence has been utilized and interpreted in
watershed studies because using such new technology has resulted in precise outcomes
compared to those of earlier studies. To obtain a basic idea of the general demographics
in research publications on DOM fluorescence for the field of watershed studies, a
literature search was conducted using the keywords dissolved organic matter, watershed,
and fluorescence. As per the results, the United States of America (USA) was the leading
publisher for the past 10 years (218 articles), followed by China (124 articles),
Canada (64 articles), South Korea (32 articles), and Japan (18 articles) (Figure 2). For the past five years, a total of 197 publications have directly mentioned the
use of DOM fluorescence in the field of watershed studies. Specifically, there were
50, 47, 39, and 39 articles published in 2021, 2020, 2019, and 2018, respectively
(Figure 3).
Fig. 2. The general demographics of research publications where dissolved organic matter fluorescence has been used for watershed studies, based on the country of the research. (Clarivate: Web of Science; Analyze Results: dissolved organic matter AND watershed (All Fields) AND fluorescence (All Fields), Accessed date: 2022/09/02)
Fig. 3. The general demographics of research publications over the past 10 years where dissolved organic matter fluorescence has been used for watershed studies. (Clarivate: Web of Science; Analyze Results: dissolved organic matter AND watershed (All Fields) AND fluorescence (All Fields), Accessed date: 2022/09/02)
The literature review revealed that EEM-PARAFAC is a promising alternative method
for tracing water quality linked with DOM composition while tracking organic matter
sources in natural aquatic systems. DOM spectroscopy displayed the potential to be
a simple and fast tool for pollution-source tracking alongside water quality indices,
which were eventually utilized to diagnose the environmental and ecological status
of the watershed. In a recent correlation study of water quality indices and DOM fluorescence
data, Tang et al. (2019) demonstrated good correlations between DOM components and
water quality parameters in peri-urban and urban river watersheds (Zhangxi River and
Lu River in Ningbo, East China, respectively). From the PARAFAC, DOM was separated
into two terrestrial humic-like components and a protein-like component. The urban
watershed revealed higher terrestrial humic-like components with a lower percentage
of protein-like components (39% and 30%, respectively), whereas the peri-urban watershed
displayed an inverse trend (33% and 37%, respectively). A correlation study with fluorescence
components and water quality parameters (COD, TN, TP, and dissolved organic carbon
(DOC)) was conducted by applying redundancy analysis (RDA). A significant linear relationship
between COD and the terrestrial humic-like component was found in both watersheds,
suggesting that the terrestrial humic-like component can be used as a good COD indicator.
Tang et al. (2019) demonstrated that the pollution sources and water quality correlated
with the DOM fluorescent components and that water quality assessment can be performed
to a certain extent using DOM fluorescence components (Tang et al., 2019). DOM fluorescence
was also successfully used in a Yellow River-based study conducted by Li et al. in
China in 2021, where the relationships of CDOM with water quality indicators and trophic
state were analyzed. PARAFAC was separated into six components, with the majority
comprising four humic-like components (85.6%) and the minority comprising two protein-like
components (15.8%). Li, Pan et al. (2021) suggested that the use of the fluorescence index (FI) had a good predictive ability
for pollution detection, especially for pollutants related to nitrogen and phosphorus
nutrients in the basin (Li, Pan et al., 2021). Using DOM fluorescence as a diagnostic tool to study the environmental and ecological
status of watersheds in this aspect was also noted. This is crucial in situations
where the ecosystem is delicate and pollution traces are found at low concentrations.
Early pollution detection will ensure the safety of endemic flora and fauna as well
as the costs of management strategies. In a study on the Tibetan Plateau in 2021,
Li et al. suggested the importance of DOM fluorescence indicators as potential highly
suitable measurement parameters for the characterization of low-concentration DOM
in alpine areas (Li, Xiao et al., 2021).
Many researchers have broadened their DOM fluorescence studies not only to track the
pollution source but also to explore the spatiotemporal variation in DOM to determine
whether it will provide insight into the land use gradient of the watershed. The spatial
variation in DOM and land use gradient studies have always provided a general trend
of a higher ratio of humic-like components when anthropogenic activity is limited,
along with a moderate or low ratio of protein-like components in the presence of human
activities. In an FDOM analysis study of a coastal river basin in eastern North Carolina,
USA; Bhattacharya and Osburn (2020) discussed the effect of land use and land cover morphology reflect on DOM composition
using FEEM-PARAFAC. During the study period, the large coastal river network was subjected
to rapid and intense land-use and land-cover changes. The results indicated prominent
terrestrially derived DOM, with the most significant control on DOM composition and
concentration in the wetland area of the study. The DOM in the wetland areas and agricultural
coastal streams were abundant in humic-like substances and structurally complex. In
comparison, mixed urbanized and forested streams were found to have abundant less
complex, low-molecular-weight DOM, along with higher concentrations of DOC and nitrogen
due to higher urban runoff and higher DOM production. From the correlation studies,
the authors concluded that increasing anthropogenic alterations had a higher tendency
to increase the abundance of reactive DOM in coastal rivers and estuaries, resulting
in severe water quality issues and that DOM could be used as an effective tool to
analyze land-use gradients in larger river systems (Bhattacharya and Osburn, 2020).
Lyu et al. (2021) carried out a four-year observation dataset of EEMs from urban and non-urban waters
in Jilin Province, northeastern China. Being one of the longest continuations of data
collection for FEEM PARAFAC studies, this study was significant. The authors compared
two watersheds and classified them into urban and non-urban areas to analyze the impact
of nonpoint source urban inputs on the DOM amount, composition, and source. The results
indicated that urbanization had an important influence on DOM concentration and composition,
specifically that urban areas had higher DOM content, CDOM absorption, DOM fluorescence
intensity, and a greater proportion of protein-like components (26% > 21.3%). In addition,
the observed proportion of humic-like components was smaller in the urban water samples
than in the non-urban samples (51.9% < 57.6%). The study revealed that the continuous
increase in impervious artificial surfaces caused by urban expansion contributed to
the increase in DOM quantity, which altered the DOM to contain more protein-like components
(Lyu et al., 2021). In a study of Three Gorges Reservoir (TGR) regions in China, Ma and Li investigated
the spatial variations in DOM compositions and sources using EEM-PARAFAC. In the samples
of forest-affected river areas, DOM revealed higher terrestrial sources and weaker
microbial sources, irrespective of hydrological seasonality. In contrast, the DOM
in farmland-affected rivers showed a more protein-like signal. The investigators concluded
that anthropogenic activities and land use were the driving factors of DOM quality
variation in the TGR region (Ma and Li, 2020).
The trend in seasonal DOM variation is affected by sunlight availability and the general
increase in temperature. Therefore, in the wet season, higher levels of overall DOM
concentration, as well as a comparatively lower ratio of protein-like components,
are typically observed if there is no recognized point source of pollution. In Lyu et al. (2021), using a four-year observation dataset of EEMs from Jilin Province, northeast China,
long-term observations of urbanized DOM reflected the response to regional climate.
Summer seasons are characterized by high overall concentrations of DOM and mixed DOM
sources. For example, the FI values revealed both the presence of autochthonous production
originating from algal growth and allochthonous input resulting from rainfall (Lyu et al., 2021). Similarly, data from the TGR region (Ma and Li, 2020) implied a higher ratio of humic acid to fulvic acid (more terrestrial origin), aromaticity,
molecular weight, and CDOM proportion in the wet season than in the dry season. The
study concluded that monsoonal precipitation was one of the driving factors of DOM
quality variation in the TGR region.
Jin et al. (2022) found that DOM in the North Canal River (China) watershed was composed of two humic
acid-like components (excitation 230 nm, emission 335/400 nm and excitation 260 nm,
emission 360/450 nm) and a tryptophan-like component (excitation/emission 280/290–350
nm). The study was conducted across four seasons throughout the year to determine
the source of DOM and its relationship to water quality parameters, along with the
spatiotemporal variation in DOM fluorescence. The intensity of DOM showed obvious
seasonal variations, with the overall DOM concentration in winter being significantly
higher than that in hotter months. The authors explained the reasons for this temporal
variation in the overall water volume and temperature factors that can chemically
change DOM. The spatial variation in the tryptophan-like component showed a significantly
higher concentration in the mainstream. The main DOM sources were human habitation
and agricultural nonpoint sources in the main channel, as well as terrestrial and
microbiological in the tributaries. The DOM composition was associated with water
quality indicators such as TN and TP concentrations (r = 0.38–0.91) (Jin et al., 2022).
Close associations between total nutrient concentration (mostly TN and TP) and fluorescent
humic-like components were observed in multiple watershed studies. This reoccurring
relationship is common in open water sources with significant human impact. Zhao et
al. (2017) conducted a correlation analysis between the spatial distribution of CDOMs
and water quality in 19 lakes across the Songhua River Basin, situated in the semi-arid
regions of northeastern China. The data imply a positive linear correlation between
the fluorescent component C1 (humic-like) and TN (R2 = 0.76 and 0.81, p < 0.01) because organic nitrogen was derived from terrestrial
humic-like substances. Similar correlation was also observed in the lakes of the Yungui
Plateau in China, which has been reported by Zhang et al. (2010) in the Ebinur Lake watershed (r = 0.61), and by Wang et al. (2017) in the Northeastern Basin (r = 0.60–0.84) in China. These results indicate that large
amounts of nitrogen are connected to carbon in the form of organic nitrogen by chemical
bonding to form the molecular structures of the humic-like components (Wang et al., 2017; Zhang et al., 2010).
UV spectroscopy has also been widely used to estimate the composition and sources
of DOM. A study conducted in Sanggou Bay, China, by Wang et al. in 2017 suggested a strong correlation between the amount of bioavailable DOC and protein-like
components separated using FEEM-PARAFAC. This study demonstrates the reliability of
estimating DOC concentration using the absorption at 280 nm (A280) in protein-like component-rich ecosystems, such as aquaculture systems (Wang et al., 2017). A five-river-based optical analysis in Japan indicated that the main types of fDOM
observed in the rivers were terrestrial humic-like and tryptophan-like substances.
The river flowed mainly through an urban area that was found to be contaminated with
other compounds, such as fluorescent whitening agents, autochthonous humic-like substances,
and extracellular polymeric substances. The slope ratio was strongly correlated with
the land use gradient and river flow. Therefore, the slope ratio S275-295 can be used as an index of pollution levels in these Japanese rivers (Ayeni et al., 2022). Similarly, a Yellow River-based study in China (2022) suggested the use of a combination
of the CDOM absorption at 254 nm (A254), spectral slope ratio (SR), specific UV absorbance at 254 nm (SUVA254), and FI as good predictive tools for the key water quality indicators TN, dissolved
total nitrogen, TP, and dissolved total phosphorus. This research implies the use
of UV spectral parameters for rapid water quality monitoring and pollution source
indication, especially for pollutants related to nitrogen and phosphorus nutrients
in polluted river basins (Li, Pan et al., 2021).
In recent years, many watershed analyses have been conducted using methodologies related
to FDOM analysis. In this review, a few recent studies are discussed in terms of their
usage and significance. A summary of the outcomes of this review is presented in Table
4. It is crucial to note that researchers tend to highlight the applicability of research
outcomes to specific watershed systems because relevance on the universal scale still
needs to be studied.
Table 4. Summary of key research studies discussed in this review
List of publication
|
Location
|
Watershed type
|
Purpose
|
Key outcomes and conclusions of the research
|
Jin et al. (2022) |
The North Canal River watershed, northern China
|
Forest- and industrial -dominated land use
|
To investigate the content, spatiotemporal fluctuations, and major sources of DOM To study the relationship between DOM composition, concentration, and water quality
|
Temporal variation: DOM concentration in winter is the highest Spatial variation:
Tryptophan-like components were significantly higher in the mainstream and the humic-like
components were higher in the tributaries Source tracking: Main-stream - human-derived point sources and agricultural nonpoint sources Tributaries - terrestrial nonpoint sourcesDOM composition is significantly related
to WQ indicators, especially TN and TP
|
Li, Xiao et al. (2021) |
Namco Lake, Niyaqu basin in the Tibetan Plateau
|
Watershed with the land cover gradient of the ice sheet, through the wetland to the
estuary
|
To investigate the content, spatiotemporal fluctuations, and major sources of DOM To evaluate the potential of FDOM as a detector for nonpoint source pollution
|
Humic-like signals: natural organic matter background or degradation products Tyrosine-like signals: pollution traces Tryptophan-like signals: microbial byproducts Wetlands can absorb or degrade the organics to regulate water quality and buffer the
environmental impact.Fluorescence indicators: for characterization of low-concentration
DOM in alpine areas; Has a potential use in environmental assessment and modeling.
|
Lyu et al. (2021) |
Jilin province, northeastern China
|
Urban and non-urban watersheds with significantly different land use and land cover
gradients
|
To characterize DOM and CDOM absorption in urban water bodies To investigate the content, spatiotemporal fluctuations, and major sources of DOM
|
DOM responds to the regional climate. Higher DOM amount and FI appeared in the summer due to autochthonous production from
algae growth and allochthonous input from rainfall.Urbanization influences DOM concentration
and composition; urban areas had higher DOM content, CDOM absorption, and DOM fluorescence
intensity (FI), higher protein-like fluorescence components
|
Li, Lu et al. (2021) |
The Yellow River, Northern China
|
Natural sediment-laden river segments and reservoirs
|
To identify possible CDOM sources in the mainstream To study the potential use of CDOM as a WQ indicator
|
Prominent humic-like component: nonpoint source erosion origin Minor protein-like components: point source discharges, anthropogenic activities The fluorescence index (FI) is a good predictor of TN in the basin
|
He et al. (2021)
|
Southern Qinling mountains in southern Shaanxi province, China
|
A series of hilly ponds with different eutrophication levels and adjacent watersheds
|
To study the potential use of FDOM as a WQ and eutrophication level indicator To identify the effects of land-use changes on aquatic DOM concentration and composition
|
A majority of humic-like components: derived from terrestrial plant decomposition
or soil organic matter Microbial humic-like component: produced by microbial decomposition Protein-like components: point source pollution, sewage discharge Farmlands are the major contributors to DOC concentration rather than forest and grasslandHumic-like
fluorescence components in A254 could be used as indicators to reflect the eutrophication level
|
Ma and Li (2020) |
Three Gorges Reservoir (TGR) region, the upper reach of the Yangtze River, China
|
Farmland and forested land use
|
To investigate the content, spatiotemporal fluctuations, and major sources of DOM To identify the effects of land-use changes on aquatic DOM concentration and composition
|
Land use and monsoonal rainfall affect DOM composition. Dry season: Lower ratio of humic acid to fulvic acid, DOM aromaticity, humification,
the molecular weight of humic substances Wet season: weaker microbial and stronger terrestrial sources in DOM regardless of
land use Forest-affected rivers (dry season): A higher degree of humification and aromaticity,
the molecular size of DOM, and a higher proportion of CDOM Farmland-affected rivers: lower molecular weight of DOM, higher FI and BIX, regardless
of hydrological seasonality
|
Tang et al. (2019)
|
Zhangxi River and Lu River watershed, Ningbo, China
|
Peri-urban and urban watershed
|
To identify the effects of urbanization on aquatic DOM concentration and composition
|
COD concentration is positively correlated with humic-like fluorescent components:
humic-like components are a good COD predictor. Urban: higher terrestrial humic-like components than protein-like components Peri-urban: inverse trend compared to urban
|
Bhattacharya and Osburn (2020) |
Neuse RiverBasin, NorthCarolina, USA
|
Coastal river basin with a variation in land use; urban, agricultural, forested, and
wetland
|
To investigate the molecular complexity and molecular weight change of aquatic DOM
across the land-use gradient To identify the effects of urbanization on the spatial variation in aquatic DOM concentration
and composition
|
Terrestrially derived the overall DOM composition and concentration Wetland and agricultural coastal streams have abundant structurally complex DOMMixed
urbanized and forested streams have abundant less complex, low molecular weight DOM;
higher concentrations of DOC and TN caused by urban runoff; and higher DOM production
|
Zhang and Liang (2019)
|
Quanchengwu Village, Luniao Town, Yuhang District, Hangzhou, Zhejiang, China
|
The East Tiaoxi River watershed This river originates from the hills within this watershed: a closed watershedAgricultural
and non-urban
|
To evaluate the potential of FDOM as a detector for nonpoint source pollution To study the potential use of FDOM as a disinfected byproduct formation potential
(DBP FP) indicator
|
Agricultural and rural nonpoint sources contribute a substantial organic pollution
load to downstream watersheds FDOM can replace the labor-intensive and time-consuming routine parameters of pollution
detectionWhen combined with the support vector machine (SVM), it can be used to indicate
pollution and predict DBP FP
|
Zhao et al. (2017)
|
Songnen Plain and Hulun Buir Plateau in semiarid regions of northeastern China
|
Fresh water and brackish water lakes: various land use/cover (e.g., cropland, grassland, forest, and residents)
|
To characterize CDOM composition To investigate CDOM differences between freshwater and brackish-water lakesTo assess
the effects on FDOM components by land cover and a point source of pollution
|
No significant differences in CDOM components between freshwater and brackish-water
lakes DOM components were affected by the spatial variation in land cover and pollution
sources in hypereutrophic brackish-water lakes. A positive linear correlation between the humic-like fluorescent component and TN
(R2 = 0.76 and 0.81, p < 0.01): organic nitrogen was derived from terrestrial humic-like
substances
|
Note: WQ indicates Water Quality.
|
5. Conclusion
DOM is an important parameter for watershed studies. The practice of using DOM in
watershed studies has been known to the scientific community for decades and is still
utilized to a great extent. The advancement of data processing/management instrumentation
and methods has resulted in many improvements in the field of DOM fluorescence analysis.
Research results provide convincing scientific evidence for water quality monitoring
and pollution control in watersheds using DOM fluorescence as an analytical tool.
A number of results implied a unique correlation between water quality parameters,
DOM fluorescent components, and optical indices. As DOM displays unique compositional
characteristics, it is crucial to verify the environmental relevance of each study
in accordance with the focused DOM types in terms of comparisons, correlations, and
concluding. Most of the recent watershed research studies compared environments to
reveal distinct varieties of DOM, as in urban vs. non-urban, urban vs. forest, or
agricultural vs. forest, without focusing on a single watershed. Research from the
past five years has shown the tendency to attribute more fluorescence and spectral
indices to a wide array of new parameters, such as microplastics of different types,
antibiotics, and specific bacterial contaminants. Most novel approaches have considered
machine learning and model development for easier predictions to improve sustainable
watershed management in the future.