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Article history: During early 2000, a new analytical procedure for nitrate isotopic measurement, termed
Received 7 September 2012 the “denitrifier method”, was established. With the development of the nitrate isotope
Received in revised form tracer method, much research has been reported detailing sources of groundwater nitrate
4 February 2013 and denitrification mechanisms. However, a shortcoming of these tracer studies has been
Accepted 7 February 2013 indicated owing to some overlapping of isotope compositions among different source
Available online 19 February 2013 materials and denitrification trends. In order to reduce these uncertainties, we examined
nitrate isotope ratios within a frame of “regional groundwater flow dynamics” to eliminate
Keywords: unnecessary uncertainties in elucidating nitrate sources and behaviors. A total of 361
Groundwater samples were collected from the Kumamoto area: the circulated groundwater system with
Flow dynamics a scale of 103 km2 in southern Japan. Subsequently, the nitrate pollution was examined
Nitrate pollution within the above-mentioned framework. As a result, a reasonable identification of the
Stable isotope ratios sources and attenuation behaviors (both denitrification and dilution) of groundwater ni-
Denitrification trate pollution was obtained over the study area. This study demonstrates that the use of
nitrate isotope tracers efficiently improves with a comprehensive understanding of
groundwater flow dynamics. The approach emphasized in this study is important and
should be applicable in other areas.
ª 2013 Elsevier Ltd. All rights reserved.
nitrate isotope tracer method has become established as a (chemical fertilizers, manures, and sewage water) taken from
better tracing tool and has increasingly been applied in many the Kumamoto area. These data were used within a tracer
parts of the world (i.e. Umezawa et al., 2008; Otero et al., 2009; study in the context of groundwater flow dynamics. We firstly
Hosono et al., 2011a). tried to understand the general view of the origins of ground-
Within a nitrate isotope tracing study, the pollution sour- water nitrate pollution, and then examined detailed attenua-
ces can be estimated by isotopic comparison between the tion mechanisms along the flow paths by denitrification as
water samples and possible source materials (Kendall, 1998). well as by mixing of the different source water. The results
The isotopic comparison can also be used as a denitrification from these investigations were used to emphasis the useful-
indicator by analyzing isotopic enrichment trends of water ness of the above approach for reducing uncertainties
samples (Kendall, 1998). However, source distinguishment encountered in previous studies, which is the prime objective
becomes difficult when different possible source materials, of this study. The approach could be applicable in future
such as manure and sewage, have a similar isotope signature studies for a better understanding of the sources and attenu-
(Xue et al., 2009; Fenech et al., 2012; Minet et al., 2012). More- ation mechanisms of groundwater nitrate pollution.
over, if isotopic compositions overlap between the source
characteristics and denitrification trends, this distinction be-
comes difficult (Xue et al., 2009). These difficulties complicate 2. Outline of the research area
data interpretation. Therefore, it has recently been argued
that a new approach and concept are needed to reduce the 2.1. Topography and climate
above mentioned shortcomings in nitrate isotope tracer
studies (Xue et al., 2009; Fenech et al., 2012; Minet et al., 2012). The Kumamoto groundwater area is defined as an area
In a circulated groundwater system, dissolved nitrate is (945 km2) surrounded by the divide of the Shira River water-
introduced to groundwater at the recharge zone and trans- shed to the north, the Midori River to the south, the Aso
ported through the lateral flow zone to the discharge zone Mountain (1592 m) to the east, and the Ariake Sea and Kinpo
within a frame of “groundwater flow dynamics” (Böhlke and Mountain (665 m) to the west (Fig. 1a). The altitude of this area
Denver, 1995; Böhlke et al., 2002; Hosono et al., 2011b). tends to decrease westward from land to ocean. Importantly,
Therefore, having a good understanding of the three- volcano-pyroclastic and lava flow deposits derived at the time
dimensional groundwater flow pathway is very important of the Aso Caldera formation formed three major highlands
when tracing complicated nitrate sources and behaviors using with altitudes around 100 m: the Kikuchi and Takayubaru
a nitrate isotope tracer. In addition, it is important to prepare highlands extending westwards and the Ueki highlands to the
detailed land-use information for the target area, especially north of the Kumamoto area (Fig. 1a). In addition, volcanic
for the assessment of potential impacts from manure and flow deposits of the Pre-Aso activity formed small hills in the
sewage (Xue et al., 2009; Fenech et al., 2012; Minet et al., 2012). central area such as Tatsuta Mountain (Fig. 1a). Kumamoto
The nitrate isotope tracer study method with a combined use had an average annual temperature and precipitation of
of the above mentioned control information appears to be an 16.9 C and 1986 mm, respectively during 1980e2010. The
efficient approach for reducing uncertainties in the past study. rainy season occurs from JuneeJuly with around 40% of the
However, emphasis has not been clearly placed on its total annual precipitation occurring during this period.
importance in previous articles.
Kumamoto City is located in the central part of the Kyushu 2.2. Geology
Islands in southern Japan. The city is known as the largest
groundwater utilization region in Japan where about one The study area is composed of four major geological constit-
million people in and around the city depend entirely on uents (Fig. 2): the Paleozoic basement of metamorphic and
groundwater for drinking purpose (Oshima, 2010; Shimada, sedimentary rocks; the Pre-Aso volcanic rocks of Tertiar-
2012). However, the monitoring data for groundwater quality yeQuaternary age; the Quaternary Aso volcanic rocks; and
show that nitrate concentrations have been increasing since overlaying alluvium deposits. Paleozoic basement rocks do
1970s (Tomiie et al., 2009, 2011). For example, NO 3 concen- not outcrop at the surface within the study area. The Pre-Aso
trations for some wells (Fig. 1a) increased by a factor of 2e7 volcanic rocks generally consist of lavas and tuff breccia (Ono
during the last 40 years (Appendix 1). Although nitrate source and Watanabe, 1985; Miyoshi et al., 2009), while the Aso vol-
controls have been implemented since the 1990s, such as canic rocks are composed of pyroclastic deposits and flow
control of fertilizer applications and the construction of bar- lavas (Ono and Watanabe, 1985). The former rocks are present
riers around manure storage sites, groundwater NO 3 is still at/around the Kinpo and Tatsuta Mountains (Fig. 1a), while
increasing and becoming an increasingly serious environ- latter rocks are distributed around the eastern side of the
mental issue (Kumamoto Prefecture and Kumamoto City, Kinpo Mountain and the western side of the Aso Caldera. Both
2005; Kumamoto City Waterworks and Sewerage Bureau, rock types have a wide chemical range between basalticer-
2008; Kumamoto City, 2009; Oshima, 2010). However, the hyolitic compositions (Ono and Watanabe, 1985; Miyoshi
principal causes of the pollution and natural attenuation et al., 2009). The Aso volcanic rocks are subdivided into four
mechanisms have not been fully understood. units according to eruption stages: Aso-1 (270 ka); Aso-2 (140
This study presents a comprehensive amount of nitrate ka); Aso-3 (120 ka); and Aso-4 (89 ka) (Ono and Watanabe,
isotope data (total of 361 samples) for groundwater (confined 1985). Of these, the Aso-2 unit is unique in its composition
and unconfined) and comparison water (spring and river of andesitic lava with joints and porous structures. It is also
water) during different seasons, and possible source materials important to note that clay impermeable layers of lacustrine
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5 2663
Fig. 1 e A map showing (a) topography and major groundwater flows and (b) land-use and sampling locations in the
Kumamoto area. Solid contour lines with numbers in Fig. 1a represent groundwater levels (m, above sea level) calculated
with a groundwater flow model using a surface and subsurface coupling flow simulator (GETFLOWS: Tosaka et al., 2000).
Details for groundwater flow model will be shown in separated paper.
sediments are widely distributed between the Aso-3 and Aso- areas becoming major groundwater recharge sources within
4 units (Fig. 2). The other clay layer of marine origin, the Ariake Kumamoto (Kumamoto Prefecture and Kumamoto City, 1995;
clay layer, is distributed over the Kumamoto plain especially Taniguchi et al., 2003). From a hydrogeological point of view,
within the coastal zone. the Aso volcanic rocks and alluvial sedimentary deposits are
the major aquifers which overlie impermeable Paleozoic
2.3. Hydrogeology basement and Pre-Aso volcanic rocks (Kumamoto Prefecture
and Kumamoto City, 1995) (Fig. 2). The aquifers are divided
The highly permeable structure of Aso-4 pyroclastic deposits into two main types: unconfined and confined aquifers (Fig. 2).
at the Ueki, Kikuchi, and Takayubaru highlands result in these The former aquifer type is composed of unwelded Aso-4
2664 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5
Fig. 2 e Hydrogeological cross sections between AeA0 and BeB0 in Fig. 1. Arrow in the figures represents groundwater flow
direction at each grid obtained by the results of a groundwater flow model calculation using a surface and subsurface
coupling flow simulator (GETFLOWS: Tosaka et al., 2000). Size of arrow corresponds to relative velocity of groundwater flow.
Values for estimated enrichment factor ε are also shown in figures for each groundwater flow zone (see text for details).
pyroclastic and alluvial sedimentary deposits, which overlie groundwater modeling (Figs. 1a and 2). The most significant
an aquiclude of impermeable lacustrine sediment layer. The flow system of confined groundwater is the flow AeA0 in Figs.
latter aquifer type consists of Aso-2 porous andesitic lava and 1a and 2. This main flow can be classified into 4 zones (Figs. 1a
pyroclastic deposits of Aso-1, Aso-2, and Aso-3 units. As an and 2): A1- the flow from the recharge area of the Kikuchi
important consideration, the aquiclude is not continuously highland to the mid-stream area of the Shira River; A2- the
distributed under the mid-stream area of the Shira River (Figs. mixing zone of groundwater from zone A1, recharged water
1a and 2). Due to the very high downward infiltration capacity from the Takayubaru highlands and the southwestern feet of
of this area (w500 mm d1), a large amount of water is Aso Mountain, and the recharged water from the Shira River;
recharged from the river into the deep aquifer (Tanaka et al., A3 e the southwestern lateral flow through the Aso-2 volcanic
2010) (Fig. 2). Groundwater is situated generally at w50 m lava aquifer toward the discharge area of the Ezu Lake with a
under the surface for unconfined and around 60e200 m for discharge rate of 1.5 108 m3 y1 (Shimada, 2012); and A4 e
confined aquifers. The groundwater levels for both aquifers the flow from the discharge area to the coastal stagnant area.
show 5e10 m seasonal change during a year. In general, the The flow BeB0 is the other important confined groundwater
high water season is from AugusteNovember and low water flow system within the study area (Figs. 1a and 2), which can be
season is from JanuaryeApril. classified into 3 zones along the flow direction: B1 e southward
flow from the recharge area of the Ueki highlands to the point of
2.4. Groundwater flow and age basement lifting; B2 e the flow across the basement uplifting
toward the entrance of plain area; and B3 e southwestward
Groundwater flow systems are well understood within the flow to the coastal stagnant area. The number of the monitoring
study area based on long-term water level monitoring and wells for the unconfined groundwater is limited compared to
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5 2665
Fig. 4 e Seasonal comparison between the high and low water season for (a) NOL 15 18 15
3 , (b) d NNO3 , (c) d ONO3 , and (d) dual d NNO3
18
and d ONO3 compositions. Two solid lines in Fig. 4d represent isotopic fractionation trends during denitrification with
d15 NNO3 :d18 ONO3 of 1.3:1 and 2.1:1, respectively.
expressed relative to atmospheric nitrogen for nitrogen and samples (n ¼ 239) exceeded the World Health Organization
Vienna Standard Mean Ocean Water (V-SMOW) for oxygen. limit of 50 mg l1. Therefore, current nitrate concentration
Isotope values were calibrated using the United States Geological level was judged to be generally lower than environmental
Society (USGS) and International Atomic Energy Agency (IAEA) criteria, although increasing trend of concentrations is a
internationally recognized nitrate standards: USGS-34, USGS-35, threat to its drinking water supply in future for many bore-
and IAEA-N3. Based on replicate measurements of standards hole sites (Tomiie et al., 2009, 2011) (Appendix 1). Similar
and samples (n ¼ 288), the analytical precisions for d15 NNO3 and frequency patterns were observed for nitrate concentrations
d18 ONO3 were better than 0.2& and 0.3&, respectively. The between confined and unconfined groundwaters (Fig. 3). The
nitrogen isotope ratio for powdered samples was determined by groundwater tended to be more NO 3 enriched than river
mass spectrometry interfaced with a CNS elemental analyzer water but showed a similar concentration range to spring
(Thermo Fisher Flash 2000). Analytical precision of the analysis water (Fig. 3). NO 3 concentrations basically were not
was better than 0.15&. changed between water samples collected at high and low
water seasons (Fig. 4a). The highest NO 3 concentrations for
both confined and unconfined groundwater samples were
4. Results found in the recharge areas at the Ueki, Kikuchi, and
Takayubaru highlands where vegetable and livestock farms
4.1. Nitrate concentrations are highly concentrated (Fig. 5a). It was also observed that
NO 3 concentrations clearly decreased along the ground-
The groundwater NO
3 concentrations ranged between 0 and water flow path from rechargeedischarge/stagnant zones
73 mg l1 and only 3 samples among the total analyzed (Fig. 5a).
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5 2667
The d15 NNO3 and d18 ONO3 of groundwater samples ranged be-
tween 6e46& and 3e48&, respectively (Fig. 6). An isotopic
compositional gap was not found between confined and un-
confined groundwaters (Fig. 6). Groundwater samples with
moderate to high NO 3 concentrations tended to have narrow
isotope compositions (d15 NNO3 ¼ 2e8& and d18 ONO3 ¼ 3e5&)
(Fig. 6), which are similar to the compositional ranges of
spring water samples. In contrast, the samples with the
lowest NO 3 concentrations tended to have higher isotopic
compositions (d15 NNO3 ¼ 8e46& and d18 ONO3 ¼ 5e48&), sug-
gesting the occurrence of denitrification. The spring and river
water d18 ONO3 compositions were similar to each other,
whereas d15 NNO3 compositions of river water were clearly
higher than those of spring water (Fig. 6).
Seasonal gaps of d15 NNO3 and d18 ONO3 were not observed for
all water samples, except groundwater samples showing
highly fractionated signatures (Fig. 4b and c). These ground-
water samples were unique in that the fractionation ratios of
d18 ONO3 to d15 NNO3 were highly variable (Fig. 4d). It has been
commonly thought that the fractionation ratio of
d15 NNO3 :d18 ONO3 during denitrification ranges within 1.3e2.1:1
(Aravena and Robertson, 1998; Mengis et al., 1999; Böttcher
et al., 1990; Fukada et al., 2003). However, some groundwater
samples collected in our study showed more variable ratios
than the reported range (Figs. 4 and 6). In fact, the cause of
variability of fractionation ratios is becoming recognized as a
matter of discussion (Kool et al., 2011), which mechanism has
not been solved yet. This will not be discussed in this paper;
however, results of this study suggest that d15 NNO3 and d18 ONO3
values of groundwater should be regarded as subject of vari-
ation during denitrification over different seasons. The
calculation of the average value is one of the approaches of
data treatment as shown in this study.
The nitrogen isotope ratios of the possible source materials
showed their own signatures with some compositional vari-
ations (Fig. 6). Remarkable isotopic compositional changes
within collected fertilizer samples were not found among
different production companies, type of farm products used
for, and sampling areas. Similarly, isotope compositions of
manure samples did not change depending on their sampling
areas. Moreover, no isotopic changing tendencies were
observed for sewage waters collected at different conditions.
It could be considered from these observations that nitrogen
isotope variation for each source material regards as isotopic
heterogeneity of material itself, but is not due to the factors of
space and probably of time.
The compositional range of d15N for chemical fertilizers
was similar to that of groundwater samples showing high
NO 1
3 concentrations (>30 mg l ), whereas sewage and
manure samples showed higher values (Fig. 6). The
groundwater samples tended to increase in d15 NNO3 (and
d18 ONO3 ) with decreasing of NO 3 and DO concentrations
along the flow direction from rechargeedischarge/stagnant
zones (Fig. 5). The pollutant input locations of manure with
high d15 NNO3 should be in/around the recharge highlands
area. The results indicated that increasing groundwater Fig. 5 e Distribution map for (a) NOL 15
3 , (b) d NNO3 , and (c) DO
d15 NNO3 in the plain and coastal areas is not due to the in the study area. Arrows indicate the major flow
contribution of manures. directions of the confined groundwater.
2668 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5
Fig. 6 e Nitrate isotope comparison for water samples with possible source references. Note that the data shown with an
asterisk are taken from Hirohata et al. (1999).
to the vegetable farms. However, with the fact that these high
5. Discussion nitrate water samples showed some d15 NNO3 variation (2e8&)
partial contributions of manures from livestock farms and
5.1. Source of nitrate pollution in groundwater organic fertilizers cannot be neglected.
One confined groundwater sample at the recharge area
It is clear from the observed nitrate distributions (Fig. 5a) that showed a high d15 NNO3 (14.9&) and NO 1
3 (31 mg l ) content
groundwater nitrate for both confined and unconfined (Fig. 6). This isotope composition corresponds with that of
groundwater with NO 3 concentrations >30 mg l
1
was manure. However, from its elevated d18 ONO3 (8.7&) value and
transported through the recharge area where vegetable and depleted DO concentration value (1.3 mg l1), it can be sug-
livestock farms are widely distributed. This groundwater is gested that the sample properties were due to the denitrifi-
characterized by DO concentration values >6 mg l1 (Fig. 5c). cation of the nitrate that originated from chemical fertilizers
Under such conditions, it is commonly considered that deni- under a sporadically anaerobic environment. The number of
trification would not preferentially occur (Spalding and Exner, houses is limited within the farming area. Even if some houses
1993; Cey et al., 1999; McCallum et al., 2008). Importantly, such are not connected to the sewer, domestic effluents generally
high NO 1 15
3 groundwater (>30 mg l ) generally has d NNO3 and drain to nearby rivers through side ditches.
18
d ONO3 compositions within 2e8& and -3e5&, respectively Leakage from sewage pipes is another possible trans-
with no significant isotopic fractionation between them portation source of domestic wastes in urbanized areas
(Fig. 6). Therefore, it can be roughly estimated that the effects (Lerner, 2002; Wakida and Lerner, 2005). In Kumamoto, the
of denitrification were not significant. From an isotopic com- downward flowing groundwater from the recharge area
parison (Fig. 6), it is most likely that concentrated nitrate of generally did not display clear tendency of NO 3 concentration
groundwater as well as those of spring water (where DO increase with an increase of d15 NNO3 in urbanized areas (Fig. 5).
concentration was in general >8 mg l1) was dominantly Therefore, it is likely that the contribution of sewage leaked
originated from long-term application of chemical fertilizers from sewage pipes is not the prime source of nitrate, although
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5 2669
some contribution of it is suggested by the analysis of chem- groundwater nitrate pollution presently observed in Kuma-
ical markers (artificial sweeteners such as acesulfame K) moto. Minor contributions of manures from livestock farms
(Nakata et al., personal communication), which is a more and organic fertilizers might also be suggested as secondary
sensible tracer of sewage source, and by the analysis with flow important sources. It is however difficult to point out their
systems (discussed later). Treated wastewater from sewage contribution rates for each sampling site due to the fact that
treatment plants, which still show high NO 3 concentrations in isotopic compositions of the source materials have their own
the order of few tens of mg l1, drain directly into nearby variations. Finer scale mixing signature of these sources
rivers. As mentioned previously, river water (with DO con- would be better expressed on a simulation model by putting
centrations >8 mg l1) showed higher d15 NNO3 compositions information of historical change of the land-use and nitrate
than do spring water and groundwater with high NO 3 loads on the groundwater flow simulation model and by
concentrations > 30 mg l1 (Fig. 6). It is reasonable to conclude tuning between calculated results and observed concentra-
that nitrate in river water was partly derived from wastewater tion and isotopic data. We are preparing to show these results
of sewage origin. in a separated paper. Our results taken in context with this
As a consequence, it can be concluded that long-term study imply that the effects of political action in the control-
application of chemical fertilizers is a prime cause of ling of fertilizer applications enforced after the 1990s are not
2670 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5
Fig. 8 e Sample plots on the d15 NNO3 vs. NOL 3 diagram for groundwater with two different nitrate attenuation types: (a)
dilution and (b) denitrification, and (c) for the Midori River watershed named as zone C groundwater. Plots for dilution type
groundwater samples are also shown in Fig. 8b in a yellow color. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5 2671
yet evident. Groundwater nitrate monitoring along with Toward the end of zone A4, confined groundwater samples
d15 NNO3 and d18 ONO3 analysis is important not only to check displayed a decline of NO 3 concentration with a decreasing
pollution status but also to evaluate the effects of manure, of DO concentration (Fig. 7a). However, d15 NNO3 fractionation
which might be the next additional concern as a pollution was not observed and clear evidence of denitrification was
source. not confirmed. Therefore, this might be interpreted to be
owing to the weakening of pollution influence to the deep
part of stagnant groundwater. In contrast, unconfined
5.2. Two different attenuation mechanisms: dilution groundwater samples showed an increasing trend of d15 NNO3
and denitrification with the decreasing of DO and NO 3 concentrations along
the flow direction (Fig. 7a). It was the only evidence of the
The contrasting decline tendency in NO 3 concentration and occurrence of denitrification within the groundwater flow
d15 NNO3 changes were observed along the flow direction be- system AeA0 .
tween the two different groundwater flow systems: AeA0 and
BeB0 (Fig. 7). This implies that different attenuation processes 5.2.2. Groundwater flow BeB0
for nitrate pollution are occurring within each flow system. A clear decline of NO 1
3 concentrations (50e1 mg l ) with the
This section describes the attenuation mechanisms for each flow direction was confirmed for zone B1 confined ground-
flow system in detail and compares their efficiencies in terms water accompanied with a major decrease of DO concentra-
of attenuation functions. tion values (8e1 mg l1) and the increasing of d15 NNO3 values
(4e8&) (Fig. 7b). This indicates the progress of the denitrifi-
5.2.1. Groundwater flow AeA0 cation reaction (Knowles, 1982; Hiscock et al., 1991; Korom,
In zone A1, nitrate concentration found in confined ground- 1992; Mariotti, 1986). At the entrance of zone 2B over the
water decreased along the flow direction (Fig. 7a). However, basement uplifting point, the water NO 3 and DO concentra-
the DO concentration values were still higher than 8 mg l1 tions increased to 20 mg l1 and 7 mg l1, respectively, while
and the d15 NNO3 change was very small (1e1.5&). Moreover, the d15 NNO3 decreased to 3& (Fig. 7b). It appears likely that
isotopic fractionation was also unclear for d18 ONO3 (Fig. 7a). In water with dissolved materials could be transported through
turn, it is well known that paddy irrigation water of the Shira the thinning part of the aquifer and the discontinuity of the
River water (NO 3 ¼ 5e6 mg l1, d15 NNO3 ¼ 7e10&, aquiclude (Fig. 2). Subsequently, through the flow toward
1
DO ¼ 8e9 mg l ) recharges underneath groundwater at the beneath the Shira River, groundwater NO 3 declined again
mid-stream area of the Shira River (Tanaka et al., 2010) (Fig. 2). (20e1.5 mg l1) with a very sudden depression of DO
These observations suggest that the NO 3 concentration in (7e1 mg l1) and with a major increase of d15 NNO3 (up to 40& in
groundwater decreased along the flow direction due to maximum) (Fig. 7b), showing clear evidence for the drastic
dispersion and/or dilution by irrigation water, but not by progress of the denitrification reaction. This zone is situated
denitrification. Water quality within the zone A2 largely var- under a topographical changing point where the terrestrial
ied (Fig. 7a), mainly due to the zone A2 being a mixing zone hills meet with plain area covered by marine and flood sedi-
among several different types of water. However, the d15 NNO3 ments (Figs. 1a and 2). Considering that marine clays and flood
compositions were homogeneous (1.5e5.5&) with the range deposits are more enriched in organic materials than igneous
almost equivalent to that of zone A1 (3.4e5.0&) (Fig. 7a). rocks and with its low DO feature, this area is regarded as a
Observed heterogeneity in NO 3 concentrations should not be denitrification hotspot similar to a riparian zone where sig-
due to denitrification but to the mixing of different water of nificant denitrification preferentially occurs (Böhlke and
varying NO 3 concentrations. Denver, 1995; Böhlke et al., 2002; Hoffmann et al., 2006). This
It is notable that NO 3 concentration in confined ground- area is termed a “hills-plain border zone”.
water gently decreased from 20 to 15 mg l1 with a small in- After water passes this zone, the d15 NNO3 composition
crease of d15 NNO3 (w6&) through zone A3 flow (Fig. 7a). The DO returns again to low values between 0 and 10& at the entrance
concentration values of groundwater averaged around of zone 3B (Fig. 7b). This indicates the scenario that the ma-
8 mg l1 throughout the zone, supporting the idea that deni- jority of nitrate from zone 1Be2B has been consumed by
trification is not a controlling factor in the decline of nitrate denitrification and has not reached this point. The NO 3 con-
concentrations. Nagai et al. (1983) revealed from water centration was low under the Shira River area (around
chemistry data that confined groundwater in this zone is the 1 mg l1). Naturally occurring nitrate in the aquifer geology
mixture of up-gradient groundwater and Shira River water might be the origin of this modestly concentrated nitrate. In
with a proportion of about 3e4:6e7. Considering our results in zone 3B, NO 3 concentrations in confined groundwater
the context of this fact, it can be concluded that the observed decreased (w0 mg l1) with a significant increase of d15 NNO3 up
decline in NO 15
3 concentrations and the increase in d NNO3 are to 30& (Fig. 7b). Groundwater in this zone is in addition
attributed to dilution by Shira River water of relatively lower characterized by low DO concentration values generally
NO 15
3 concentration and higher d NNO3 value (average of <2 mg l1, suggesting the occurrence of denitrification. A
5.5 mg l1 and 7.9&, respectively; n ¼ 2), which is recharged at small influence of nitrate infiltration from the unsaturated
the mid-stream area of this river. In Fig. 7a, water chemistry zone was confirmed in zone 3B; however, the general ten-
and nitrate isotopic profiles from zone A1eA3 appear similar dency of changing patterns of NO 15
3 , DO, and d NNO3 for un-
between confined and unconfined groundwater, suggesting confined groundwater was quite similar to that of confined
that similar processes explained above were also taking place groundwater throughout the flow distance (Fig. 7b). Therefore,
for unconfined groundwater. similar processes should be affecting both groundwater types.
2672 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5
5.2.3. Efficiencies of the two different attenuation functions Several approaches for tracing the source of groundwater ni-
Fig. 8 compares the effects of the two different attenuation trate pollution have recently been proposed, for instance, the
types on groundwater nitrate pollution judged in the previ- use of chemical markers (Fenech et al., 2012) and application
ous discussion: dilution (Fig. 8a) and denitrification (Fig. 8b). of other stable isotope tracers (Vengosh et al., 2002; Widory
Groundwater for both attenuation types showed highest et al., 2004; Xue et al., 2009; Hosono et al., 2010, 2011a) in
NO 1
3 concentrations around 50 mg l , which were largely addition to d15 NNO3 and d18 ONO3 . These tracers are definitely
derived from chemical fertilizers. The NO 3 concentrations useful for achieving a comprehensive understanding of the
decreased to 20e10 mg l1 for most of the samples attenu- nitrate pollution mechanisms. However, in a strict sense these
ated by the dilution with lower nitrate water (Fig. 8a). From tracers can be useful under the hypothesis that they can be
the plots distribution in Fig. 8a and previous discussion, it used as a proxy of nitrate. Therefore, seeking a more efficient
could be suggested that the lower nitrate water is the use of nitrate isotope tracers is still important as it is the only
mixture of the least contaminated (or non-contaminated) direct fingerprint of tracing nitrate sources and recording the
groundwaters and the recharged river waters moderately occurrence of denitrification.
w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5 2673
With the traditional way of utilizing d15N and d18O tracers be more vulnerable to additional pollution. Aspects regarding
on d15 NNO3 vs. d18 ONO3 and NO 15
3 vs. d NNO3 diagrams (Fig. 6), it to these natural attenuation potentialities should be infor-
was difficult to separate the two types of anthropogenic ni- mative for future groundwater resource exploration and
trate sources (chemical fertilizers and treated wastewater preservation. This study demonstrated that traceability of
from sewage treatment plants derived through recharging nitrate isotope ratios can be improved by the combined use of
river water) and also two types of attenuation processes land-use and groundwater flow information. The proposed
(dilution and denitrification) for Kumamoto groundwater, approach should be applicable for future investigations in
since all samples are plotted within similar compositions other regions.
(Figs. 6 and 8). In contrast, the analysis taking into account
detailed groundwater flows enables us to separate the effects
of the mixing of different sources and denitrification (Fig. 8).
Our study clearly demonstrated that the nitrate isotopic Acknowledgments
traceability significantly improves with the understanding of
groundwater flow dynamics. We thank Mr. Satoshi Sakaeda and Mr. Masaaki Hirohata of
the Kumamoto Prefectural Government for their help during
field surveys. We also thank Prof. Yasunori Kawagoshi of the
Department of Civil & Environmental Engineering, Kuma-
7. Conclusions
moto University, for a fruitful discussion. Groundwater flow
models used in this study were constructed under the
Our study revealed that the application of chemical fertilizers
operation of the Geosphere Environmental Technology Cor-
is a prime cause of groundwater nitrate pollution in Kuma-
poration, Tokyo, Japan. This study was funded by a CREST
moto. Nitrogen load from manure was not detected as being
Project (JST: Japan Science and Technology Agency) with
the dominant source of pollution. However, this effect should
additional support from the Grant-in-Aid for Young Scien-
be checked during future monitoring programs, since the
tists (A) (no. 24681007).
number of livestock farms has increased in more recent years.
Polluted groundwater is attenuated along the flow distance
from recharge through lateral flow to the discharge (or stag-
nant) zone by two different processes: dilution and denitrifi-
cation. About 60e80% and 98% of nitrate of anthropogenic Appendix 1. Figure showing increaseL1
of nitrate
origin were assumed to be purified by dilution and denitrifi- concentrations (vertical axis; mg l as NOL3 LN)
cation, respectively. Denitrification was evaluated as the more with time (horizontal axis; year) in confined
efficient attenuation function and the hills-plain border zone groundwater at selected borehole sites in
has the highest attenuation potential over the area. In Kumamoto area (modified after Tomiie et al.,
contrast, the groundwater attenuated by dilution appears to 2011).
2674 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 2 6 6 1 e2 6 7 5