STOTEN-21961; No of Pages 10

Science of the Total Environment xxx (2017) xxxxxx

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

New insights into the source of decadal increase in chemical oxygen

demand associated with dissolved organic carbon in Dianchi Lake

Wei Guo a, Feng Yang b, Yanping Li b, Shengrui Wang b,c,

a
School of Environmental and Chemical Engineering, North China Electric Power University, Beijing, 102206, China
b
State Key Laboratory of Environmental Criteria and Risk Assessment, State Environmental Protection Key Laboratory for Lake Pollution Control, Research Center of Lake Eco-environment,
Chinese Research Academy of Environmental Sciences, Beijing 100012, China
c
Yunnan Key Laboratory of Pollution Process and Management of Plateau Lake Watershed, Kunming, Yunnan Province, 650034, China.

H I G H L I G H T S G R A P H I C A L A B S T R A C T

Agricultural runoff and urban runoff

were the main sources of DOC in the
lake.
A large quantity of refractory DOC from
sewage tail accumulated in the lake.
Urbanization construction in the water-
shed increased the input of DOC to the
lake.

a r t i c l e i n f o a b s t r a c t

Article history: Dissolved organic carbon (DOC) can be used an alternative index of water quality instead of chemical oxygen de-
Received 8 December 2016 mand (COD) to reect the organic pollution in water. The monitoring data of water quality in a long-term (1990
Received in revised form 1 February 2017 2013) from Dianchi Lake conrmed the increase trend of COD concentration in the lake since 2007. The similar-
Accepted 3 February 2017
ities and differences in the DOC components between the lake and its sources and the contribution from alloch-
Available online xxxx
thonous and autochthonous DOC to the total DOC in this lake were determined to elucidate the reason of COD
Editor: Jay Gan increase based on C/N atomic ratios, stable isotope abundance of carbon and nitrogen, UVvisible spectroscopy,
three-dimensional excitationemission matrix (3DEEM) uorescence spectroscopy. The terrigenous organic
Keywords: matter showed humic-like uorescence, and the autochthonous organic matter showed tryptophan-like compo-
Chemical demand oxygen nents. Agricultural runoff (9.5%), leaf litter (7.5%) and urban runoff (13.2%) were the main sources of DOC in the
Dissolved organic matter lake. Sewage tail was a major source of organic materials, 3DEEM for the indicates that sewage tail DOC compo-
Fluorescence spectroscopy sition did not change markedly over the biodegradation period, indicating that sewage tail contains a high load of
Dianchi Lake DOC that is resistant to further biodegradation and subsequently accumulates in the lake. The change of land use
Land use
in the catchment and the increase of sewage tail load into the lake are the key factors for the increase in COD con-
centration in Dianchi Lake. Thus, the lake should be protected by controlling the pollution from the urban non-
point sources and refractory composition in point sources.
2017 Elsevier B.V. All rights reserved.

Corresponding author at: State Key Laboratory of Environmental Criteria and Risk Assessment, State Environmental Protection Key Laboratory for Lake Pollution Control, Research
Center of Lake Eco-environment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China.
E-mail address: wangsr@craes.org.cn (S. Wang).

http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
0048-9697/ 2017 Elsevier B.V. All rights reserved.

Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
2 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx
1. Introduction
Chemical oxygen demand (COD) is an important indicator of organic
pollution and reducing substances in surface water and is generally
used as a water environmental quality parameter to describe organic
pollution (Aoki et al., 2004). Recently, dissolved organic carbon (DOC)
is also being used as another index of organic pollution in water
(Nguyen and Hur, 2011; Spencer et al., 2012). With urban development
and industrialization, a large quantity of refractory organic materials is
discharged into the lakes and rivers by the input from nonpoint and
point sources, causing DOC or COD accumulation and increase in surface
waters and other pollution problems such as eutrophication (Hongve
et al., 2004; Francis et al., 2007; Landre et al., 2009). Dianchi Lake, the
sixth largest freshwater lake in China, known as the Pearl of the
Highland was facing the problem of water quality deterioration due
to urbanization near the catchment in recent year (Huang et al.,
2014). The increase of COD was also observed in the last decade al-
though a lot of manpower and material resources were spent to control
the organic pollution from point and nonpoint sources (Wang, 2015).
Herein, to clarify the reason for the increase in COD, it is important to
analyze the structural and chemical characteristics of DOC from differ-
ent sources and their contributions to the DOC in this lake.
There are two categories regarding the sources of DOC in lakes.
Allochthonous DOC is primarily derived from terrestrial input including
rivers, plant litter, and soil (Nguyen and Hur, 2011; SanClements et al.,
2012). Autochthonous DOC is mainly derived from the release of
macrophytes, phytoplankton, and macroalgae in their growth or
decomposition stages and sediments (Qu et al., 2013). Compared to
autochthonous DOC, allochthonous DOC derived from eld soil and
treated sewage had a high resistance to further degradation and easy ac-
cumulation in lakes (Nguyen and Hur, 2011). The changes in land use
within the catchment associated with urbanization and climatic
warming signicantly affect the source and fate of allochthonous DOC
in lakes (Chen et al., 2012; Oni et al., 2014). In this regard, the tracing
of allochthonous and autochthonous DOC sources in lakes may provide
essential information about the organic pollution in lake water.
Currently, UVvisible and uorescence spectroscopic methods are
used to determine the composition and structure of DOC in lakes
(Zhang et al., 2009; Nguyen and Hur, 2011; Chen et al., 2012). The ratios
of absorption at 254 nm and 285 nm for a DOC concentration, specic
UV absorption SUVA254 and SUVA285, respectively, and adsorption
ratio A250/A365 (AR) showed that photochemically and microbially
decomposed DOC had a lower molecular weight and aromaticity, and
the aromatic DOC increased with the increasing percentage of peatland
and forests in the catchment of Lake Vrtsjrv in 20082010 (Piirsoo
et al., 2012). An increase in runoff increased the mobilization of organic
matters and thus increased the COD export from soils to lakes (Saarinen
et al., 2010). The DOC derived from macrophyte and algae DOC contrib-
utes only 710% of DOC in lakes; the DOC component showed tyrosine-
like matter (Chen et al., 2012). However, these studies mostly focused
on the contribution of single sources to the DOC in lakes such as alloch-
thonous or autochthonous sources and neglected potential effects of en-
tire watershed input including allochthonous and autochthonous DOC
to the composition and behavior of DOC in lakes. In addition, because
of the complexity and heterogeneity of DOC and the differences in la-
custrine catchment development, the reasons for the increase in COD
related to DOC are complex.
Therefore, in this study, the DOC structural and chemical character-
istics of different sources DOC including allochthonous sources such as
forest soil and leaf litter, compost, eld soil, treated sewage and its trib-
utaries, and autochthonous sources such as sediment and algae across
the watershed in the Dianchi Lake were analyzed and evaluated. The ob-
jectives of this study were: (1) to compare the structure and behavior of
different sources of the lake DOC; (2) to analyze the major sources of the
lake DOC and refractory DOC; (3) to clarify the probably effects of wa-
tershed change on the increase of COD in the lake.
Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
2. Material and methods
2.1. Sample collection
Dianchi Lake (24272527 N, 1022910301 E) is the largest
freshwater lake in Yunnan-Guizhou Plateau; it is a very important lake
in southwestern China for sheries, bird habitat, water resources, and
regional environment and economics, located near Kunming City of
Yunnan province (Fig. 1). The water area of the lake is ~298 km2. The
water in the lake has a maximum depth of 10.1 m and an average
depth of 4.1 m. The catchment area of the lake is ~2920 km2. The land
use in this watershed in 2013 includes 43.4% forest, 25.1% farmland,
11.1% water, 19.7% urban, and 0.8% pasture. The average annual
evaporation (1409 mm) in the lake is signicantly higher than the aver-
age annual precipitation (924 mm). The lake is mainly fed by the runoff
of N 29 rivers and sewage tail from wastewater treatment plants. The av-
erage annual water quantity into the lake from the agricultural area in-
cluding Dongdahe River, Chai River, Dahe River etc. was approximately
1.8 108 m3, and that from the urban area including Panlongjiang River,
Luolonghe River, Baoxianghe River etc. was approximately 5.2 108 m3,
and the discharge quantity of the sewage was 3.8 108 m3. The popula-
tion density of the catchment exceeding 1200 persons/km2 is higher
than that of Taihu Lake watershed (1000 persons/km2) and signicantly
higher than that of Lake Biwa catchment (350 persons/km2). Dianchi
Lake Basin accounts for approximately 0.8% of the land area of Yunnan
Province; this basin generates roughly 24% of the GDP and houses 10%
of the population. Water quality within Dianchi Lake is under pressure
from the increasing population and change in land use within the lake's
catchment.
According to the land use and economic types in the watershed, the
allochthonous pollution mainly arises from three areas, forest area,
farmland area, and urban area, by natural and anthropogenic activities
(Fig. 1). Sampling was carried out on July 2013. During the period be-
tween July and August, DOC in lake is typically affected by autochtho-
nous sources and allochthonous sources (Zhang et al., 2014). In the
forest area, woodland soil (WS) and leaf litter (LL) were sampled from
three typical forests sites including Laoeshan, Guanyinshan North and
Guanyinshan (Wang, 2015). In the farmland area, compost (CP) and
eld soil (FS) were sampled from three typical agricultural cultivation
and livestock breeding area including Haikou, Dianchi South and
Xinjiezhen, and agricultural runoff (AR) were sampled from three rivers
including Dongdahe River, Caihe River and Dahe River (Wang, 2015). In
the urban area, urban runoff (UR) was sampled from three rivers includ-
ing Panlongjiang River, Baoxianghe River and Luolonghe River, and
sewage tail (ST) was sampled from two large wastewater treatment
plants with total treatment capacity of 300,000 t/d near the down-
stream of Panlongjiang River (Li et al., 2012; Wang, 2015). At the
same time, the samples from autochthonous sources including lake sed-
iment (LS) and lake algae (LA) and lake water (LW) samples were col-
lected from six locations (D1D6) from the north to the south of the
lake (Fig. 1).
2.2. DOC extraction and preparation
The samples of soil, sediment, and compost samples were freeze-
dried, ground, and passed through a 0.18 mm sieve. The leaves samples
were rst air-dried and cut into pieces of approximately 1 cm2 and then
shredded to further reduce their size. For algal, 30 L lake water sample
was collected and then was centrifuged at 5000 rpm 15 min, and the su-
pernatant was aspirated. The algae particles samples were freeze-dried.
Then these treated solid samples including soil, sediment, compost and
leaves were mixed with distilled deionized water at a solid-to-solution
mass ratio of 1:10 for 24 h in a horizontal shaker at room temperature.
The algae samples were ultra-sonicated for 1 h by mixing the deionized
water with dried algae at a solid-to-solution mass ratio of 1:20. These
mixed extracts were centrifuged at 10000 rpm for 30 min and then
 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx 3

Fig. 1. Map of Dianchi Lake showing location of the sampling area.

were nally ltered through a 0.7 m glass ber lter (Whatman GF/F,
United Kingdom) to remove the particulates (Chen et al., 2012). For
the water samples from lake, river and sewage tail, the collected water
samples (1 L) were ltered through a 0.7 m glass ber lter to remove
the particulates. The ber lters were rinsed with distilled water before
using.
Moreover, some prepared DOC solutions were used to perform nat-
ural biodegradation experiments to obtain the degradation characteris-
tics of the DOC from these sources. The test was conducted in a sterile
5 L brown glass bottle for each DOC solution at 25 C for 31 d by gently
shaking the solution every day (Zhang et al., 2009; Nguyen and Hur,
2011). During the shaking, the bottle was aerated to prevent anaerobic
conditions (Zhang et al., 2009). A certain quantity of NaN3 (200 mg/L)
was added to the solution as sterile control samples during the experi-
ments. Thus, the remaining DOC was considered to be recalcitrant. All
the prepared water samples were nally ltered through a 0.7 m
glass ber lter to remove the particulates. The percentages of the
biodegraded carbon can be obtained by the ratio of initial concentration
of DOC to nial concentration of DOC.
2.3. Analytical methods
The data of COD, total nitrogen (TN), and total phosphorus (TP) in
lake water during 19902013 were provided by the Center for Environ-
mental Monitoring in Kunming city, Yunnan province. The COD, total ni-
trogen (TN), and total phosphorus (TP) in lake water were determined
by the acid potassium permanganate method using a UV spectropho-
tometer after digesting with alkaline potassium persulfate and molyb-
denum blue colorimetric method after digesting with potassium
persulfate (Wei et al., 2002). The DOC concentrations in the samples

Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
4 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx

were analyzed using a PerkinElmer 2400 elemental analyzer. 13Corg (5.19 109 kg) is the dried weight of surcial sediment (~ 20 cm) in
and 15N were analyzed using an isotope-ratio mass spectrometer lake, Qs of leaves (1.45 109 kg) is the weight of fallen leaves in the
(Finnigan DeltaPlus XP) with a precision of b 0.1 for 13Corg and catchment, and Qs of algae (2.53 108 kg) is the total weight of all
b0.2 for 15N (Guo et al., 2015). For 13Corg analysis, the samples kinds of algae in lake water. The Is of woodland soil, eld soil, compost,
were pretreated with 1 M HCl to remove inorganic carbon. sediment, leaves, and algae were from the empirical values of non-point
UV absorbance was measured using a UVvisible spectrophotome- source indirect inputs in the catchment in previous study (Ma and
ter (DR-5000; HACH, USA) and 1 cm quartz cuvette at wavelengths Wang, 2015; Wang, 2015), were respectively 0.74, 0.76, 0.72, 0.90,
ranging from 200 nm to 700 nm (Li et al., 2014). SUVA values were de- 0.72, and 1.0.
termined as the ratio of the UV absorbance at 254 nm for a DOC concen- The contribution of the lake from different DOC sources to overall
tration (Nguyen and Hur, 2011). A250/A365 values were calculated from DOC input into the lake was estimated using Eq. (3):
the ratio of the absorption coefcients at 250 nm and 365 nm (Zhang
et al., 2011). 3DEEM uorescence spectroscopy was performed using a
Hitachi F-7000 uorescence spectrophotometer (F-7000; Hitachi, C Li Li =Lw Ls 3
Japan) in a clear quartz cuvette (Li et al., 2014). Both the excitation
and emission slits were adjusted to 5 nm. Excitation and emission
were simultaneously scanned at wavelengths ranging from 200 nm to In the formula, CLi is the contribution of the DOC load from i source
450 nm and from 250 nm to 600 nm, respectively, at 5-nm intervals. DOC to the overall load of DOC entering into the lake (%), Li is the load
The FI was calculated as the ratio of the emission intensity at 450 nm of i source DOC entering into the lake (t/y).
to that at 500 nm for an excitation wavelength of 370 nm (McKnight
et al., 2001). The humication index (HIX) was estimated from the
ratio of the last and rst quarter regions for a uorescence emission
spectrum at the wavelengths ranging from 300 nm to 480 nm using
an excitation wavelength of 254 nm (Zsolnay et al., 1999).
Statistical analyses such as mean value were performed with SPSS
11.0 software (Statistical Program for Social Sciences). Differences in pa-
rameters between two categories were assessed with a paired t-test,
using a p value of 0.05 to determine signicance. Principal component
analysis (PCA) was used to examine the relationships between param-
eters and analyze the characteristics of DOC sources using SPSS
software.

2.4. Load estimation of different DOC sources

The DOC loadings from the autochthonous and allochthonous

sources in the lake were estimated according to the sample characteris-
tics determined from the forest, farmland, urban, and lake areas. The
followed calculation method referred to the previous research of Ma
and Wang (2015) and Wang (2015). Autochthonous DOC sources main-
ly include the release of sediment and algae. Allochthonous DOC sources
mainly include the input of river runoff, sewage tail, soil, compost, and
leaf litter. For the river and sewage, the water sample input load (Lw,
t/y) was calculated using Eq. (1):

Lw C w  1Dr  Q w  I w 1

In the formula, Cw is the concentration of DOC from river runoff or

sewage tail (mg/L), Dr. is the biodegraded carbon percentages (%), Qw
is the water quantity of rive or sewage tail entering into the lake (m3),
Iw is the input coefcients of DOC from the river or sewage tail discharge
to the lake. The value of is near 1 in the study due to the samples of river
and sewage tail were sampled in the entrance into the lake of river and
sewage tail.
For the soil, sediment, leaves, and algae, the solid sample input load
(LS, t/y) was calculated using Eq. (2):

LS C s  1Dr  Q s  Is 2

where CS is the concentration of DOC from the solid samples (mg/kg)

obtained according to the solid-to-solution mass ratios; Qs is the total
quantity of solid samples released in the catchment (kg); Is is the
input coefcient of DOC from the soil, sediment, leaves, and algae
discharged to the lake. The values of Qs and Is were from the previous re-
search in the catchment (Ma and Wang, 2015; Wang, 2015). Qs of soil is
the erosion amount of surcial woodland soil (1.41 109 kg) and eld
soil (9.90 109 kg), Qs of compost (3.98 109 kg) is the amount of Fig. 2. Total nitrogen (TN), total phosphorus (TP), and chemical oxygen demand (COD)
fecal composting produced by livestock and poultry, Qs of sediment change trends from Dianchi Lake between 1990 and 2013.

Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx 5

Table 1 (27.53), lake sediment (25.80), and lake water (23.75). C/N values
13C, 15N and C/N ratio in different sources DOC samples from Dianchi Lake. N15 are generally considered to be of low nutritional value to con-
Sample Sources 13C 15N C/N sumers and represented the terrigenous materials (Kendall et al.,
2001). Green and blue algae were the dominant phytoplankton groups
WS Woodland soil 25.88 5.40 16.80 in the sampling period. It is recognized that cyanophyta have compara-
LL Leaf litter 27.38 4.56 27.53 tively low C/N ratios due to their lack of structural tissue (Baird and
CP Compost 25.51 14.06 9.47 Middleton, 2004). For sewage tail, because a large quantity of organic
FS Field soil 24.99 7.90 10.29
compounds was removed, the value of C/N is relatively lower (3.01).
AR Agricultural runoff 23.61 10.28 14.92
UR Urban runoff 28.86 6.10 11.90 The stable carbon and nitrogen isotopic compositions of woodland
LS Lake sediment 28.15 6.55 25.80 soil, leaf litter, eld soil, urban runoff, lake sediment, and lake water
LA Lake algae 26.89 0.11 9.12 were similar (13C: from 28.86 to 24.99; 15N: from 4.56 to
ST Sewage tail 22.45 2.65 3.01 8.08), indicating that the organic matter in the lake may be mainly de-
LW Lake water 26.65 8.08 23.75
rived from terrigenous vegetation, soil, and runoff (Chen et al., 2012).
However, for lake algae, under eutrophic conditions, cyanobacteria uti-
lize nitrogen to synthesize organic matter; therefore, the value of nitro-
3. Results and discussion gen isotope is close to 0 (Cloern et al., 2002).

3.1. Change in lake water quality

The annual variability of lake water quality including TN, TP, and
COD in the period of 19902013 is shown in Fig. 2. The TN showed a
slowly increasing trend and roughly uctuated in the range of 1.5
2.0 mg/L other than several peak points such as at 1994 (2.23 mg/L),
2007 (3.01 mg/L), and 2011(2.81 mg/L). The TP showed an increasing
trend before 1999 (0.33 mg/L), but signicantly decreased and kept a
stable value (0.16 0.02 mg/L) after 2001. Compared to the historical
change in TN and TP, the change in COD with time showed three stages:
i) a high level from 1990 to 1994 (8.90 0.98 mg/L), ii) a lower level
from 1995 to 2006 (6.30 0.70 mg/L), and iii) a higher level from
2007 to 2013 (10.90 0.67 mg/L). Compared to the rst two phase,
the average concentration of COD in the phase of 20072013 is 1.22
times that in the phase of 19901994 and 1.73 times that in the phase
of 19952006. Implementation of the inhibited and limited use of
phosphate detergent and application of sewage treatment plant pol-
icy (Huang et al., 2014) since 2000 may have signicantly reduced the
TP and controlled COD and TN. However, with the rapid urbanization
development since 2008, the land use and pollution sources of the wa-
tershed signicantly changed, probably leading the concentration of
COD back to a high level.
3.2. Investigation of DOC by C/N and stable carbon isotope
C/N atomic ratios and stable carbon and nitrogen isotopes were used
to differentiate the contributions to DOC or COD in the lake from terrig-
enous origins and phytoplankton (Chen et al., 2012). The characteristics
of C/N ratios and stable carbon and nitrogen isotopes are shown in
Table 1. The values of C/N ranged between 3.01 and 27.53. The C/N ra-
tios in FS and CP were similar to those in runoff, but the values from
other sources were over 15, such as woodland soil (16.80), leaf litter
3.3. UVvisible and uorescence characteristics of different DOC sources
The characteristics changes in DOC shown in Table 2 are based on
the analysis of DOC biodegradation under natural conditions and spec-
tral features. The percentages of the biodegraded carbon for the DOC
samples from ten sources ranged from 1.81% to 74.40%. The lowest per-
centage of carbon reduction can be attributed to fewer microbial actions
for the DOC from soil sources (Nguyen and Hur, 2011). The SUVA values
for these DOC samples showed a low level (b3.0 L mg1 m1), indicat-
ing a rather low aromaticity of DOC (Piirsoo et al., 2012), and other geo-
chemical processes such as photodegradation may play roles in the
composition of lake DOC (Nguyen and Hur, 2011), particularly for the
DOC obtained from sediments, sewage tail, leaf litter, lake water, and
urban runoff. The A250:A365 ratio is related to the aromatic content
and molecular size of DOC (Peuravuori and Pihlaja, 1997); relatively
high values (4.736.00) for urban runoff, lake sediment, and lake
water provide the evidence of a higher proportion of fulvic acids (FA),
indicating a lower aromaticity (McKnight et al., 2001). The lowest and
highest mean A250:A365 values in lake algae (1.50) and urban runoff
(6.00) indicate autochthonous and allochthonous DOC, respectively
(Spencer et al., 2012; Qu et al., 2013). The measured FI values varied
from 1.45 to 2.04, sufcient to indicate signicant differences in the
source of DOM. The terrigenous DOC such as woodland soil, eld soil,
and leaf litter showed a low mean FI, whereas algal-derived DOC
showed the highest mean FI, which is consistent with the research by
Mueller et al. (2012). A large variation in HIX values was observed
among these DOC samples, ranging from 0.49 to 8.37. The higher HIX
values are related to a low percentage of oxygen-containing functional
groups (Fuentes et al., 2006), whereas the lower HIX values indicate
complex biogeochemical processes other than microbial degradation
for DOC formation (Nguyen and Hur, 2011).

Table 2
The DOC concentrations, the biodegraded carbon percentages, UVvisible and uorescence characteristics for different sources DOC in Dianchi Lake.

Sources DOC mg/L Biodegraded carbon % UVvisible spectroscopy Fluorescence spectroscopy

SUVA A250/A365 FI HIX

L/(mg1 m1)

Woodland soil (WS) 53.46 6.89 1.51 2.13 1.45 7.39

Leaf litter (LL) 437.23 48.91 0.22 2.15 1.50 1.03
Compost (CP) 68.25 1.81 1.30 2.45 1.79 8.37
Field soil (FS) 30.46 4.52 1.22 2.41 1.71 5.01
Agricultural runoff (AR) 26.17 37.14 0.50 3.59 1.76 1.28
Urban runoff (UR) 9.39 15.78 0.34 6.00 1.94 0.49
Sewage tail (ST) 38.12 6.32 0.20 2.51 1.84 2.99
Lake sediment (LS) 104.98 23.54 0.08 4.83 1.88 0.88
Lake algae (LA) 340.35 74.40 0.79 1.50 2.04 4.58
Lake water (LW) 15.15 38.23 0.22 4.73 1.87 0.77

DOC: Dissolved organic carbon; SUVA: Specic UV absorbance; A250/A365: the ratio of the adsorption coefcients at 250 nm and 365 nm; FI: Fluorescence index; HIX: Humication index.

Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
6 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx

The 3DEEM uorescence technique can signicantly distinguish the
origin of the DOC. The 3DEEM uorescence spectra of different DOC
sources in the lake are shown in Fig. 3. The peaks in the uorescence
EEMs of DOC in these samples showed many common features previ-
ously identied (Baker and Curry, 2004; Chen et al., 2012): 1) Peak A lo-
cated at the Ex/Em of 230270/360470 nm represents UV fulvic-like
composition; 2) Peak B located at the Ex/Em of 270290/300320 nm
represents tyrosine-like composition from autochthonous sources;
3) Peak C located at the Ex/Em of 310360/410460 nm represents vis-
ible humic-like composition; 4) Peak D located at the Ex/Em of
220240/280330 nm represents protein-like composition from
terrigenous sources; 5) Peak T located at the Ex/Em of 270280/320
350 nm represents tryptophan composition.
As shown in Fig. 3, the woodland soil, eld soil, and compost had the
similar kinds of peaks, Peak A and Peak C, indicating the characteristics
of terrigenous humic substances. The leaf litter and agricultural runoff
had the similar kinds of peaks, Peak A, Peak D, and Peak T, indicating
that the release DOC of terrigenous plant leaves might entered into
the agricultural river. Studies have shown rapid release of DOC and nu-
trients from submerged plant material (Qu et al., 2013). This may be in-
dicating that even in urban areas, leaf litter is still a dominant source of
DOC as shown in previously published papers (Nguyen and Hur, 2011).

Fig. 3. 3DEEM of DOC in different sources from Dianchi Lake WS: Woodland soil; LL: Leaf litter; CP: Compost; FS: Field soil; AR: Agricultural runoff; UR: Urban runoff; ST: Sewage tail; LS:
Lake sediment; LA: Lake algae.

Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx 7

Agricultural runoff and urban runoff had a similar kind of peak, Peak A, soil, and compost) to lake sediment DOC (Fig. 4b). They are located close
probably indicating that the two types of runoff have the same fulvic- to each other in the plot, exhibiting similar loadings on PC1 and PC2.
like substance input. The lake sediment had a similar kind of peak, Nonaromatic moieties and low-molecular-weight UV-absorbing compo-
Peak A with sewage tail, Peak B with lake algae, Peak D with leaf litter, nents are likely to be the main structures of the four DOC sources. In the
agricultural runoff, and lake algae, indicating that the sediment is the positive zone of PC2 and PC1, the loadings of agricultural runoff, leaf lit-
sink of humic-like and tyrosine-like organic matters including autoch- ter, and urban runoff are closer to the value of lake water according to
thonous and allochthonous sources. The differences in the uorescence the extent and sign of their loadings on PC1 and PC2, indicating that
intensity of the DOC in these samples probably indicate a change in the the DOC source of agricultural runoff, leaf litter, and urban runoff is the
DOC components in different sources. main DOC source of the lake water. Moreover, the DOC of sewage tail
contributed the main refractory components in the DOC of lake water.
3.4. Analysis of DOC source The results are consistent with the prior reports on tracking DOC sources
for other large lakes, whose water quality is signicantly affected by ag-
According to the above mentioned analysis on the characteristics of ricultural and urban tributaries (Nguyen and Hur, 2011; SanClements
different DOC sources, the composition of DOC had some differences et al., 2012). The rapid urbanization and industrialization in the water-
with each other. Thus, to better identify the source of DOC in the lake, shed might signicantly accelerate and increase these types of DOC de-
a qualitative principal component analysis (PCA) was performed by rived from agricultural runoff, leaf litter, urban runoff, and sewage tail
using SPSS software. In the study, 13C, 15N, C/N ratio, the percentages sources. Changes of vegetation types might magnitude the degree of
of the biodegraded carbon, SUVA, A250/A365, FI, and HIX were selected as soil erosion and increase the mobilization of leaf litter.
the parameters for source analysis. For the characteristics of DOC
sources, the rst two components explained over 97.63% of the total 3.5. Analysis of the contribution of allochthonous and autochthonous
data variance. The rst principal component (PC1) was responsible for DOC sources
79.53% of the variance, and the second principal component (PC2)
was responsible for 18.10% of the variance. PC1 was highly positively The input load and contribution of the lake from different DOC
correlated with the SUVA, HIX, and 15N values (N0.679) and negatively sources was estimated using Eqs. (1), (2) and (3), and the results are
correlated with the C/N and A250/A365 values. According to their load-
ings, PC1 in the positive direction probably indicate the higher aroma-
ticity for DOC, but that in the negative direction probably indicate a
lower aromaticity for DOC (Nguyen and Hur, 2011), consistent with
the analysis results for these indexes on DOC sources in the results
section. The lower values of SUVA, HIX, and 15N and the higher values
of C/N and A250/A365 indicate a lower aromaticity and refractory feature
such as in the urban runoff and lake sediment DOC. PC2 was highly pos-
itively correlated with the DOC biodegradation percentages and 13C
and negatively correlated with the C/N and A250/A365. PC2 may be
associated with a tendency of further composition transformation by
biodegradation (Nguyen and Hur, 2011). The higher values of DOC bio-
degradation rate and 13C and the lower values of C/N and A250/A365 in-
dicate easier degradation features such as in the DOC of lake algae and
leaf litter. A recent study also demonstrated that degradation processes
preferentially remove the oxidized, aromatic compounds, whereas re-
duced, aliphatic, and N-containing compounds are either resistant to
degradation or tightly cycled and thus persist in aquatic systems
(Kellerman et al., 2015).
In the plot of DOC source distribution, the rst two components ex-
plained over 96.17% of the total data variance. The PC1 was responsible
for 80.81% of the variance, and the PC2 was responsible for 15.36% of
the variance. PC1 was positively correlated with the lake algae and lake
sediment values and highly negatively correlated with the sewage tail
value. According to their loadings, PC1 in the positive direction probably
indicate a high protein-like enrichment in autochthonous DOC, but in
the negative direction probably indicate the refractory feature in anthro-
pogenic DOC. Moreover, the sewage tail had a higher loading in PC2 than
other DOC samples. The interpretation of PC2 indicates that further mi-
crobial transformation of these DOC sources possibly occurs, but the ten-
dency is probably smaller for the sewage tail compared to other DOC
samples. Fig. 3 also shows that the lake algae and lake sediment have
similar 3DEEM uorescence peak position and intensity, but the sewage
tail is substantially different than other DOC samples. The sources be-
tween one group including the leaf litter, agricultural runoff, and lake
water, and another group including the eld soil, woodland soil, and
compost, and lake sediment showed opposite loadings on PC2. This
can be attributed to the difference in the humic-like composition and rel-
ative enrichment of terrestrial plants and aquatic algae. Compared to Fig. 4. (a) Factor loading plot for the selected DOC index as the rst two principal
components; (b) Factor scores plot for different sources DOC sample as rst two
aquatic algae, terrestrial plants have more refractory components such principal components. DOC: Dissolved organic carbon; WS: Woodland soil; LL: Leaf
as cellulose and lignins (Qu et al., 2013). We found a clear characteristic litter; CP: Compost; FS: Field soil; AR: Agricultural runoff; UR: Urban runoff; ST: Sewage
indicative of the contribution of terrestrial soil DOC (eld soil, woodland tail; LS: Lake sediment; LA: Lake algae.

Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
8 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx

shown in Fig. 5. The total load input to the lake was 31,039 t/y, and
mainly derived from allochthonous DOC with a contribution ratio of
88.2% to the total DOC. The urban runoff and sewage tail of the water-
shed signicantly affected the DOC characteristics with a contribution
ratio of 57.4% to the total DOC. Moreover, leaf litter is also an important
terrestrial DOC source in the lake with a contribution ratio of 7.5% to
the total DOC, as conrmed in the lakes and streams in the USA
(SanClements et al., 2012).
In the allochthonous DOC sources, sewage tail had the largest contri-
bution (44.2%), followed by urban runoff (13.2%) and agricultural runoff
(9.5%). The higher ratio of sewage tail DOC to the total DOC can be
attributed to the following reasons: 1) sewage tail is the main supply
source of the lake and the percentages of biodegraded carbon are
lower (6.32%); 2) the outow of the lake is less because of the
semienclosed characteristic of the lake. The water is mainly lost by
evaporation. Unlike estuary and coastal waters, the DOC in the lake
was mainly derived from the input of rivers (Piirsoo et al., 2012). Ac-
cording to the analysis of 3DEEM uorescence for the main DOC input
sources such as the sewage tail and urban runoff before and after the
degradation (Figs. 3 and 5), fulvic-like uorescence peak A did not clear-
ly change, particularly in sewage tail. Only the peak position slightly
moved to backward, and the peak intensity decreased, consistent with
their natural biodegradation rate and spectral characteristics (Table 2).
This indicates that a large quantity of DOC with a relatively high resis-
tance to further degradation from the urban area might have accumu-
lated in the lake. In the autochthonous DOC sources, the contribution
of sediment release to DOC load (10.4%) is much larger than that of
the algae decomposition release (1.4%). This can be attributed to:
1) Dianchi is a semi-enclosed lake, a large quantity of suspended solids
from river runoff and sewage tail will continually sink and accumulate
in sediment; 2) some biological residues such as dying aquatic plants
and organisms will sink in the surface sediment; 3) some terrestrial
organic matter will entering into the lake under the erosion action of
wind and water and nally sink in the sediment; 4) re-suspension will
often occur under certain hydraulic action from human activities such
as shipping and biological disturbances (Wang, 2015). This is unlike
some extremely eutrophic lakes such as Taihu Lake where autochtho-
nous DOC is mainly derived from the release of macroalgae (Zhang
et al., 2011).
3.6. Effect of watershed change on COD increase
An increase in lakes' COD or DOC concentration in Europe, North
America, and East Asian countries has been observed from 1990 to

Fig. 5. The input load of different DOC sources in Dianchi Lake WS: Woodland soil; LL: Leaf litter; CP: Compost; FS: Field soil; AR: Agricultural runoff; UR: Urban runoff; ST: Sewage tail; LS:
Lake sediment; LA: Lake algae.

Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx
Fig. 6. The change of the land use, sewage discharge and rainfall in the watershed of Dianchi Lake DS: Discharge standard of sewage tail.
2005, probably caused by climate and land use (Monteith et al., 2007;
Johansson et al., 2010; Nguyen and Hur, 2011). For Dianchi Lake, the
concentration of COD during 19901994 and 20072013 had a high
level. The project of three rivers and three lakes pollution control
and Zero OClock Action including Dianchi Lake (19962005) have ef-
fectively controlled the pollution from city and industry in the catch-
ment (Zhang et al., 2014), which might lead the lower level of COD
concentration during 19952006. Although relative measurements of
improving water quality were still continually carried out in the lake,
with the signicantly increase of discharge load for sewage, the concen-
tration of COD reached back to the higher level since 2007. For the in-
crease of COD in Dianchi Lake, the effect of climate may not be
signicant; the quantity of rainfall did not signicantly increase from
1980 to 2013 (Fig. 6), only slightly uctuated on the top and bottom
of the average value (924 mm). Thus, the relative DOC contribution
from water erosion and natural river runoff such as agricultural runoff
caused by rainfall did not signicantly change the DOC from 1980 to
2013. Probably, the higher evaporation quantity might increase the
DOC concentrations because of the decrease in water level in the past
two decades (Wang, 2015).
In contrast, the relative DOC contribution from anthropogenic activ-
ities to the change in COD or DOC from 1980 to 2013 is higher. The
changes in land use within the catchment associated with urbanization
signicantly affected the source and fate of lakes' DOC characteristics
(Oni et al., 2014). The increased COD concentrations (Fig. 2) in the
lake are driven by the change in land use (Fig. 6) with increase in con-
struction land (~16.41%) and in forest land (~9.70%), and a good posi-
tive correlation was found between COD and construction land (r =
0.76, p b 0.05) or forest land (r = 0.89, p b 0.05). The increasing dis-
charge of sewage tail (~38 times) from 1980 to 2013 affected the com-
position and structure of DOC in this lake ecosystem. Urbanization
increased the city nonpoint source pollution in the lake (Huang et al.,
2014; Ma and Wang, 2015). More importantly, urbanization signicant-
ly increased the discharge of sewage tail. From 1995 to 2013, the
discharged standard of wastewater COD decreased from 60 mg/L to
50 mg/L; however, the discharged quantity of sewage tail increased
from 0.19 108 m3 to 3.84 108 m3, coupled with the refractory sec-
tions in sewage tail that could not be removed (Nguyen and Hur,
2011). According to the estimation, annual growth load of COD about
sewage tail discharge into the lake during 19901994 was 720 t/y,
that of 19952006 was 750 t/y and that of 20072013 was1420 t/y.
Please cite this article as: Guo, W., et al., New insights into the source of decadal increase in chemical oxygen demand associated with dissolved
organic carbon in Dianchi Lake, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.02.024
9
This shows that the direct effect of urban point sources on the lake
DOC was not effectively controlled since 2007, the concentration of
COD in 20072013 reached back to the higher level. Thus, the land use
change, particularly urbanization in the catchment is a key factor in
the observed increase in COD between 1990 and 2013 in Dianchi Lake.
With the rapid urban development in China, similar pollution problems
of COD or DOC increase in other lakes as Dianchi Lake might manifest
and become problematic due to the increase in urban nonpoint source
load and quantity of sewage tail and the change in the composition
and structure of DOC or COD. Therefore, the strategies and methods
for lake treatments and contamination control in China should be ad-
justed to better protect freshwater sources.
4. Conclusions
The continuous treatment and management in Dianchi Lake in the
last several decades have solved the problems of eutrophication, TN,
and TP, but several other pollution sources have increased. Urbanization
development in the watershed might signicantly accelerate and in-
crease the DOC derived from agricultural runoff, urban runoff and sew-
age tail sources exhibiting humic-like and fulvic-like uorescence. The
increased COD concentrations in the lake might be driven by the change
in land use with the increase in construction land (~16.41%) and forest
land (~9.70%) and the increasing discharge of sewage tail (~38 times)
from 1980 to 2013, affecting the composition and structure of DOC in
this lake ecosystem. The characteristics and geochemical process of
the refractory components of DOC in the lake or point sources should
be studied in the future. The lake should be managed and protected
by controlling the exogenous pollution from the urban nonpoint
sources and refractory composition in point sources and by restoring
the ecosystem functions of the lake to control the endogenous pollution
from sediment and algae.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (Grant Nos. U1202235 and 41103070), National
High-level Personnel of Special Support Program (People Plan, Grant
No. 2012002001), and Beijing Natural Science Foundation of China
(No. 8152028).
10 W. Guo et al. / Science of the Total Environment xxx (2017) xxxxxx
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