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IAHR AIIH

XXVII CONGRESO LATINOAMERICANO DE HIDRÁULICA


LIMA, PERÚ, 28 AL 30 DE SETIEMBRE DE 2016

ORGANIC CARBON TRANSPORT DURING FLOOD DUE TO RAINFALL


IN A HEADWATER CATCHMENT OF KUSHIRO WETLAND, JAPAN

Hajime Kasama1, Katsuaki Komai1, Yasuyuku Maruya2, and Keisuke Nakayama3


1
Graduate School of Civil and Environmental Engineering, Kitami Institute of Technology, 165 Koen-cho, Kitami, 090-
8507, Japan, m1652200050@std.kitami-it.ac.jp; komai@mail.kitami-it.ac.jp
2
River Basin Research Center, Gifu University, 1-1 Yanagido, Gifu, Gifu 501-1193, Japan
3
Graduate School of Engineering, Kobe University, 1-1 Rokkodai, Nada-ku, Kobe, 657-8501, Japan

RESUMEN:
Con el fin de estimar el ingreso de carbono orgánico en la tierra a la zona costera de la cuenca
boreal que contiene un humedal, se estimó la tasa de producción de carbono orgánico disuelto (DOC)
y comparado por medio de un enfoque basado en períodos de inundaciones y aguas bajas. Mediante
el uso del cromóforo de la materia orgánica disuelta (CDOM) con alta selectividad y sensibilidad, el
análisis de origen se examinó al mismo tiempo, y se examinó las características de escorrentía de
carbono orgánico disuelto en las cabeceras de los humedales de Kushiro. En la cuenca del río Kuchoro,
se ha estimado que las inundaciones tienen un impacto importante en el transporte de DOC. En el
caso de la inundación observada con una probabilidad de 1,3 años, el transporte DOC en el pico era
equivalente a aproximadamente 30 veces el transporte de DOC en aguas bajas. Se encontró que los
compuestos aromáticos, tales como lignina, que puede ser un carbono azul de la tierra tienen mayor
contribución en aguas bajas que durante la inundación en la cuenca del río Kuchoro. La fuente de
DOC puede variar con los caudales de acuerdo con los resultados obtenidos de CDOM en la cuenca
del Rio Kuchoro. En las cuencas de los ríos Kuchoro y Onnenai, a causa de la agricultura y el uso del
suelo de naturaleza rica, el transporte de sustancias derivados de suelos aumenta con el caudal y
depende de la tasa de uso del suelo en la cuenca de acuerdo a la tasa de intensidad de fluorescencia
de lpk3/lpk4, comparar significativamente con estudios previos en otra cuenca templado.

ABSTRACT:
In order to estimate organic carbon input from land to coastal zone in boreal watershed
containing wetland, production rate of dissolved organic carbon (DOC) was estimated and compared
by means of focusing on periods of flood and calm water. By using chromophoric dissolved organic
matter (CDOM) with high selectivity and sensitivity, origin analysis was examined at the same time,
and runoff characteristics of DOC in the headwaters of the Kushiro wetland was discussed. In Kutyoro
river catchment, it has been estimated that flood have a major impact on the transport of DOC. In
case of the observed flood with probability of 1.3 years, DOC transport at the peak was equivalent to
approximately 30 times of DOC transport during calm water. Aromatic compounds, such as Lignin,
which can be a blue carbon source from land was found to contribute larger during calm water than
during flood in the Kutyoro River catchment. Source of DOC can vary with flow rate according to
the results obtained from CDOM in Kutyoro River catchment. In Kutyoro and Onnenai River
catchments, because of agriculture and nature rich land use, the transport of soil-derived substances
increases with flow rate and depends on land use ratio in the catchment according to fluorescence
intensity ratio of Ipk3/Ipk4 significantly comparing with previous studies in the other temperate
catchment.

KEYWORDS: dissolved organic carbon; chromophoric dissolved organic matter; land use; boreal
watershed; wetland
Figs. 1.- Japan and Kushiro coastal zone Figs. 2.- Kutyoro and Onnenai Rivers’ water
catchment area. Dashed line is water
catchment area.

Table 1.- Land use of headwater catchments


Station Pasture(㎢) Forest(㎢) Wetland(㎢) Farmland(㎢)
K1 18.244 71.376 0.42 1.22
K2 14.257 69.028 0.27 1.22
K3 6.147 52.948 0 0.224
O1 1.753 10.46 0.105 0.002
O2 0.051 0.408 0 0
O3 0.588 7.346 0.074 0
O4 0 0.382 0 0

INTRODUCTION

In Kushiro coastal zone which is the most famous specialty areas of kelp in Japan, Oyashio,
cold current (Figs. 1), is possibly one of the major nutrient sources. On the other hand, its hinterland
consists of the headwaters of Lake Kussharo, domestic leading farming area, and the widest wetland
in Japan. Organic carbon originated from various sources is supplied from the hinterland though the
Kushiro coastal zone. In particular, since peat soil in wetlands contains rich organic carbon that has
been accumulated by corrosion of terrestrial plants, peat soil can be one of the major sources of
organic carbon that accumulated in ocean and coastal ecosystem (so-called blue carbon); however,
its contribution has been not clarified yet. In the present study, in order to estimate organic carbon
input from land to coastal zone, production rate of dissolved organic carbon (hereinafter, referred to
as DOC) was estimated and compared by means of focusing on the periods of flood and calm water.
By using chromophoric dissolved organic matter (hereinafter, referred to as CDOM) with high
selectivity and sensitivity, origin analysis was examined at the same time, runoff characteristics of
DOC in the headwaters of the Kushiro wetland was discussed.

METHODS

Sampling
Fig. 2 shows headwater catchments of Kushiro wetland, upstream reach of Kutyoro River (K1,
K2, and K3) and Onnenai River (O1, O2, O3, and O4), and observation stations. Table 1 shows land
use data in each catchment of observation station. The observation points were placed in consideration
of land use in each small catchment. The water samples were collected during rainfall and flood from
October 14 to 15, 2014, and during calm water on October 21, 2014. The water samples during flood
were collected seven times at time intervals in 2 hours or less.

Dissolved organic carbon (DOC)


As preprocessing for TOC analysis, water samples were filtered by PTFE filter with a pore
diameter of 0.2 μm. Next, pH of the filtered samples were adjusted to 2.0 or less by adding
hydrochloric acid. Inorganic carbonate was removed by sparging treatment with high purity air, and
after that, DOC were analyzed by TOC analyzer (TOC-5000A, Shimadzu) based on combustion
catalytic oxidation method.

Suspended solid (SS)


The suction filtration was carried out glass fiber filter paper (Whatman GF/B) with preheating
by 105℃ in 2 hours. And, filter paper after filtration were dried for 24 hours at 105℃. By considering
weight of dried filter paper, SS was obtained from net collected sediment weight divided by water
volume.

Absorbance at the ultraviolet wavelength of 254 nm


Aromatics which possibly contribute to DOC have absorbance at the ultraviolet wavelength
of 254 nm (hereinafter referred to as a254). SUVA254 obtained from a254 divided by DOC concentration
is known to show a good correlation with the ratio of aromatic compound (Weishaar et al., 2003).
Therefore, SUVA254 is recognized as an indicator of organic matter derived from land in aquatic
environment (Goni et al., 2003). In the present study, a254 was measured by using an ultraviolet-
visible spectrophotometer (UVmini-1240, Shimadzu) for the calculation of SUVA254. Absorbance of
blank value was corrected by purified water.
SUVA254=a254/DOC (Lmg-1m -1) [1]

Chromophoric dissolved organic matter (CDOM)


The fluorescence intensity of CDOM was measured by using a fluorescence
spectrophotometer (FP-6200, JASCO). EEMs of the fluorescence intensity (Excitation Emission
Matrices; 3-dimensional excitation fluorescence spectrum) were obtained with a blank value of pure
water. Furthermore, Raman light of water was determined as datum fluorescence intensity for
calculation of relative fluorescence intensity (I) at six peak wavelengths of CDOM which were
reported in previous studies. Here, the peak wavelengths of relative fluorescence intensity of CDOM
are corresponding to humic acid-like substance (Em/Ex = 430 nm/240 nm: Ipk3, Em/Ex = 430 nm/345
nm: Ipk4), protein-like substance (345 nm/285 nm: Ipk6), and fulvic acid-like substance (430 nm/320
nm: Ipk7), respectively.

During the flood, the estimation of the material generated amount of each land use
Plane source load from each land use were estimated from concentrations of DOC and SS,
river discharge, and precipitation. Based on the relationship between runoff surface substances at
outflow point K and total surface substances within the catchment area of the outflow point K, as
expressed in Equation [2], the optimal production rate from each land use were determined by
multivariate analysis.
n
4
r
C jK Q K   Pij   frA iK [2]
i 1  r0  K
where, Cjk: concentration of substance j at outflow point K (mg/L), Qk: flow rate at outflow point K
(m3/s), r: rainfall in the catchment area of outflow point K (mm/h), r0: reference precipitation (mm/h),
f: runoff rate, Pij: production rate of substance j per unit area of land use i (kg/km2y), Aik: the area of
land use i in a catchment area of outflow point K (km2).
Figs. 3.- Peak values of DOC concentration (a) and a254 (b) at each station during flood and calm water.
Blue line and bar chart are peak value during flood and calm water, respectively.

Fig. 4.- Peak values of SUVA254 at each station during flood. The bar graph shows the calm water data

RESULTS

Doc, suva254, and a254 during flood


Figs. 3 and 4 show peak values of DOC concentration, SUVA254 and a254 at each station during
flood and calm water.
As shown in Fig. 3 (a), the maximum peak values of DOC concentration during flood was 9.7
mg/L at O2 in the Onnenai River. In contrast, during calm water, DOC concentration at the highest
was 1.57 mg/L at O1 even in Onnenai River where DOC concentration was relatively higher than in
Kutyoro River. Moreover, DOC concentration in Kutyoro River was only 0.76 mg/L during calm
water at K3, uppermost stream of the river. In terms of concentration pattern of DOC, few differences
in DOC concentration in Onnenai River were observed among the stations during calm water. In
contrast, in Kutyoro River, DOC concentration increased in the downstream direction during calm
water. As a result, at every station, peak values of DOC concentrations during flood are at least three
times higher than during calm water.
As shown in Fig. 3 (b), peak values of a254 during flood in Kutyoro River tend to be higher
in downstream reach than in upstream reach as is the case with DOC concentration (Fig. 3 (a)). During
flood, peak value of a254 was in maximum at O2. In contrast, during calm water, there were few
differences in the downstream direction.
Figs. 5. - Temporal variation of the flow rate (a) and DOC concentrations (b) during flood

Figs. 6.- Relative fluorescence intensity during flood and calm water at stations K1 and K3 in Kutyoro River
((a) K1 during calm water, (b) K1 during flood, (c) K3 during calm water, (d) K3 during flood)

Fig. 4 indicates that peak values of SUVA254 during flood have deviation and do not exceed
those of calm water. Peak value of SUVA254 at K2 during flood was 1.625 L mg-1 m -1 in the minimum
of Kutyoro River.

Temporal variations in flow rate and DOC concentration during flood


Figs. 5 show temporal variations in flow rate and DOC concentration during flood. Flow rate
peak was approximately at 18pm. In comparison with Onnenai River (O1, O2, O3, and O4), the
increase of DOC concentration were in good agreement with increase of flow rate in Kutyoro River
(K1, K2, and K3). In addition, DOC concentration at the beginning of field observation (14-16pm,
October 14) at O2 and O4 during flood had been already higher than those of calm water (October
21); that is, DOC peaks appeared earlier at O2 and O4 than at other stations.
Figs. 7.- Relative fluorescence intensities of CDOMs during flood and calm water (Ipk3, Ipk4: humic acid-like
substances, Ipk6: protein like substances, Ipk7: fulvic acid-like substances)

Excitation emission matrices (EEMS)


Figs. 6 show relative fluorescence intensity during flood and calm water at stations K1 and
K3 in Kutyoro River. Straight solid line shows position of Raman light of water. Isolines and color
show relative fluorescence intensity. Alphabetic characters with subscript number show humic acid-
like substances (H1: pk3; H2: pk4), protein-like substances (P4: pk6), and fulvic acid-like substance
(F5: pk7). Although it can be confirmed that weak peak at of H1 appear during calm water in Figs. (a)
and (c), a prominent peak appeared in the same wavelength range during flood. Moreover, during
flood in Figs. (c) and (d), clear peak was confirmed near F1.

Comparison of CDOM during flood and calm water


Figs. 7 show comparison of CDOM (pk3, pk4, pk6, and pk7) during flood and calm water. In
all CDOM peaks, relative fluorescence intensities were stronger during flood than during calm water.
Trend of the distribution of (a) humic acid-like substance (Ipk3 and Ipk4) and (d) fulvic acid-like
substance (Ipk7) are similar; Both during flood and calm water, the relative fluorescence intensities
were strong in the downstream reach of the Onnenai River, and weak in the upstream reach in the
Kutyoro River, respectively. However, in particular, the relative fluorescence intensity at O3 only
increases during flood in humic acid-like substances (pk3). In terms of the trend of the distribution of
a humic acid-like substance (a) pk3 and (b) pk4, the relative fluorescence intensity in pk3 differs
among observation points more clearly than in pk4, during flood as well as calm water. Moreover,
the difference in the relative fluorescence intensity at Onnenai River is stronger than that of Kutyoro
River, not only during calm water but also during flood. In comparison with peak values during flood,
the runoff amount of humic-like substances differ approximately twice among stations.
Although protein-like substances (Ipk6) shown in Fig. (c) were stronger during flood than
during calm water, the relative fluorescence intensity during flood increased in Onnenai River than
in Kutyoro River, and presents different tendency, comparing with humic acid-like and fulvic acid-
like substances.

Temporal variation of CDOM during flood


Figs. 8 show temporal variations of relative fluorescence intensity of CDOM during flood at
all observation stations. Ipk3 fluctuated significantly with flow rate. Ipk4 remains always around 15.
Figs. 8.- Temporal variations of relative Figs. 9.- Temporal variations in SS and DOC
fluorescence intensity at all observation concentration during flood. Left: Kutyoro
stations during flood River, Right: Onnenai River

Fig. 10.- Reproduce a result of the amount of generation of DOC

Ipk7 did not vary with flow rate (Fig. 5 (a)) in contrast to Ipk3. In addition, Ipk3 and Ipk7 show prominent
relative fluorescence intensity compared to the other peaks of CDOM.

DISCUSSIONS

Response of DOC to flow rate variation


As shown in Figs. 5, DOC in Kutyoro River (K1, K2, and K3) varies well with flow rate,
comparing with Onnenai River. As a result of regression analysis of flow rate and DOC concentration,
weak correlation with correlation coefficient R> 0.65 was observed in Kutyoro River. In contrast,
little correlation with R> 0.21 was observed in Onnenai River. In present study, in which flood return
period was 1.3 years, peak values of DOC transport during flood was 29.6*10-3 mg/s, equivalent to
approximately 30 times of DOC transport during calm water (1.13 * 10-3 mg/s). Consequently, DOC
transport was possibly impacted by flood in Kutyoro River catchment.

Comparison of transport characteristics and production rate in DOC and SS


Figs. 9 show temporal variations in SS and DOC concentration during flood in Kutyoro and
Onnenai Rivers. Although SS in Kutyoro River at any station decreased continuously after their peaks.
Figs. 11.- Ratio of CDOM and DOC in calm water Figs. 12.- Temporal variations in ratio of CDOM
and DOC during flood

Table 2.- Incidence of SS and DOC in each land use


Pasture Forest Wetland Farmland
2
SS(kg/㎞ y) 199.89 33.0537 338.292 341.225
2
DOC(kg/㎞ y) 0.0003 4.93788 93.7545 0.00758858

In contrast, DOC concentration did not decrease immediately after their peaks and remained higher
than during calm water (Fig. 3 (a)).
At O4 shown in Fig. 9 (b), peak of SS in Onnenai River occurred fast relatively, according to
the fact that SS decrease sharply from 80 mg/L to less than 20 mg/L in short period of time between
the first and the second water samplings; DOC concentration remains high after the decrease of SS.
Fig 10 shows calculation results of DOC transport estimated from Equation (2), where pr0
and n are 5 mm/h and 0.01, respectively. In calculation results, correlation coefficient was R> 0.40.
As shown in Table 2, estimated production rates of SS and DOC in each land use have different
pattern. DOC transport possibly influences during flood in the long term, since the fact that high DOC
concentration retained longer during flood than during calm water even after peak of flow rate.

Transport properties of aromatic compounds

In Fig. 3 (a), DOC is larger at the flood peaks than during calm water, particularly in Onnenai
River. In contrast, since SUVA254 is associated with aromatic compounds derived from plant, such as
lignin, Fig. 4 suggests that the aromatic compounds contribute to DOC during flood, being different
from that of calm water. Therefore, although DOC transport from the headwaters of Kushiro impacts
largely during flood, aromatic compounds derived from plant, such as lignin, which can be blue
carbon alternatively (Watanabe et al, 2013) derived from the land, contribute less during flood than
in clam water.

Characterization of effluent water by CDOM


Next, constituents of CDOM at the time of flood will be discussed. Figs. 11 and 12 show
Ipk3/DOC, Ipk7/DOC, and Ipk3/Ipk4 at the time of clam water (October 21, 2014) and flood (October 14-
15, 2014), respectively.
From the results of Ipk3/DOC, it was found that the percentage of humic acid-like substances
in flood period (Fig. 11 (b)) was larger than at the time of clam water (Fig. 12 (b)). That is, constituents
of DOM derived from different land use area vary with flow rate, not constantly discharged in the
catchment.
Furthermore, it has been reported that the higher Ipk3/Ipk4 appears, shown in Fig. 11 (c), the
more soil-derived substances contains such as humics and pore water in peat soil (Coble, 2013;
Sugiyama et al, 2005). Here, Ipk3/Ipk4 was regarded as an indicator of soil-derived substances. In
previous studies in Sakura River and Koise River in Japan, Ipk3/Ipk4 was reported as approximately
0.5 in August. In contrast, the average value during floods in Kutyoro and Onnenai Rivers catchment
was twice or more than their report. The catchment of Sakura and Koise Rivers contain less forest,
pasture, and wetland area (Jiayun L.I. et al. 2011), and those of Kutyoro and Onnenai Rivers contain
more forest, pasture, and wetland area. Therefore, high Ipk3/Ipk4 were likely associated with these rich
humic area as a plane source of soil-derived substances in Kutyoro and Onnenai river catchments. As
a result, in Kutyoro and Onnenai Rivers, soil-derived substances seem to be contained more than
Sakura and Koise Rivers. In addition, the inputs of soil-derived substances were almost the same in
the order of magnitude at any stations during flood. At stations K3, O1, and O4, Ipk3/Ipk4, varying
larger than the other stations, suggests that the influence of soil-derived substances is affected by land
use ratio in the catchment.
Consequently, in Kutyoro and Onnenai Rivers, CDOM variation indicates that the source of
DOC likely changes during flood. That is, temporal variation of organic matter during flood can be
depicted by the fluorescence intensity rate of Ipk3 and Ipk4 as in soil-derived substances.

CONCLUSIONS

In the present study, organic carbon transport in the headwater catchment of Kushiro wetland
was assessed and discussed.
(1) In Kutyoro river catchment, it has been estimated that flood have a major impact on the transport
of DOC. In case of the flood with probability of 1.3 years in the present study, DOC transport at
the peak was equivalent to approximately 30 times of DOC transport during calm water.
(2) Aromatic compounds, such as Lignin, which are of interest and can be a blue carbon from land
was found to contribute larger during calm water than during flood in the Kutyoro River
catchment.
(3) Source of DOC can vary with flow rate according to the results obtained from CDOM in Kutyoro
River catchment.
(4) In Kutyoro and Onnenai River catchments, because of agriculture and nature rich land use, the
transport of soil-derived substances increases with flow rate and depends on land use ratio in the
catchment according to fluorescence intensity ratio of Ipk3/Ipk4 significantly comparing with
previous studies in the other temperate catchment.

Acknowledgement: This study was supported by JSPS KAKENHI Grant Number JP15K00514. A
part of the observed water quality data and water samples were provided by Kushiro Development
and Construction Department, Hokkaido Regional Development Bureau, Japan. Precipitation data
used in runoff analysis were obtained from Japan Meteorological Agency. The authors would like to
thank all these collaborators.

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