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Earth and Space Science

RESEARCH ARTICLE
10.1002/2015EA000117
Key Points:
Groundwater in claypan watersheds
was more susceptible to NO3-N
contamination
Preferential pathways were the
primary mechanism for NO3-N
movement to groundwater
Hydraulic conductivity controlled
NO3-N distributions over strata in
the aquifer

Correspondence to:
O. M. Al-Qudah,
al-qudaho@lincolnu.edu

Citation:
Al-Qudah, O. M., F. Liu, R. N. Lerch,
N. Kitchen, and J. Yang (2016), Controls
on nitrate-N concentrations in
groundwater in a Missourian claypan
watershed, Earth and Space Science, 3,
90105, doi:10.1002/2015EA000117.
Received 20 MAY 2015
Accepted 22 OCT 2015
Accepted article online 28 OCT 2015
Published online 6 MAR 2016

Controls on nitrate-N concentrations in groundwater

in a Missourian claypan watershed
Omar M. Al-Qudah1, Fengjing Liu1, Robert N. Lerch2, Newell Kitchen2, and John Yang1
1

Department of Agriculture and Environmental Science and Cooperative Research Program, Lincoln University, Jefferson
City, Missouri, USA, 2Cropping Systems and Water Quality Research Unit, USDA-ARS, Columbia, Missouri, USA

Abstract Nitrogen (N) fertilizer applications have resulted in widespread groundwater nitrate-N (NO3-N)
contamination in the U.S. Corn Belt. Goodwater Creek Experimental Watershed (GCEW) is an agricultural
watershed in the claypan soil region of northeastern Missouri with a network of 96 wells at depths of 2.715.7 m.
The objectives of this study were to (1) inspect the spatial and temporal variations of NO3-N concentrations
in GCEWs groundwater, particularly with well depth at scales ranging from individual well, well nest,
and eld to the entire watershed during the period 1991 to 2004; (2) understand the processes controlling
the variability of NO3-N concentrations in groundwater at various scales within GCEW; and (3) compare
groundwater NO3-N concentrations in GCEW to other agricultural watersheds in the U.S. Nitrate-N concentrations
were determined in more than 2000 samples collected from 1991 to 2004. Despite the low hydraulic
conductivity of the claypan soils, considerable NO3-N contamination of the glacial till aquifer occurred, with
38% of the wells exceeding 10 mg L 1. Groundwater recharge by preferential pathways through the claypan
appeared to be the primary mechanism for NO3-N movement to the aquifer. Changes in concentration with
depth steadily increased to 8.510 m and then decreased with further depth. This pattern was consistent
with decreased hydraulic conductivity in the Paleosol layer at 8.510 m, denitrication below this layer, and
mixing of recent contaminated water with older uncontaminated water in the lowest strata. Only 1923% of
sampled wells exceeded 10 mg L 1 in nonclaypan agricultural watersheds over the continental U.S.,
suggesting that groundwater in GCEW was more susceptible to NO3-N contamination than nonclaypan
watersheds. These results demonstrated that preferential ow through the soil and hydraulic conductivity
of the subsurface strata controlled NO3-N transport in this claypan watershed.
1. Introduction
Withdrawals of groundwater have increased and are expected to continue rising as the population increases
and the availability of surface water becomes increasingly limited with a changing climate [Healy, 2010;
Follett, 1989]. Not only does quantity but also the quality of groundwater affects the long-term sustainable
use of groundwater resources, especially in intense agricultural regions, where the urban and rural population,
irrigation, and industries have relied on groundwater as their major water supplies [Noland and Stoner, 2000].
The intense applications of fertilizers in agricultural regions have resulted in severe groundwater contamination,
particularly nitrogen [e.g., Burow et al., 2010; DeSimone, 2009; Lerch et al., 2005; Kitchen et al., 1997; Wilkinson
and Maley, 1996]. Therefore, understanding the controls on nitrogen concentrations in groundwater is very
important for protecting groundwater resources.

2015. The Authors.

This is an open access article under the
terms of the Creative Commons
Attribution-NonCommercial-NoDerivs
License, which permits use and distribution in any medium, provided the
original work is properly cited, the use is
non-commercial and no modications
or adaptations are made.

AL-QUDAH ET AL.

Nitrogen (N) is an essential element of aquatic ecosystem, but excessive levels in groundwater, particularly in the
form of nitrate, can reduce the quality of water for human uses and lead to many environmental and health
problems. The deleterious effects of excessive environmental N include the following: (1) an oxygen decient
condition referred to as blue baby syndrome in infants under the age of 6 months [Fan and Steinberg,
1996], (2) the risk of non-Hodgkins lymphoma in adults and reduced stomach acidity [Ward et al., 1996;
Washington State Department of Health, 2005], and (3) acidication of soils and water resources [Motavalli
et al., 2008]. Because of these problems, the U.S. Environmental Protection Agency (EPA) has established a
maximum contaminant level (MCL) for NO3-N in drinking water at l0 mg L 1 [http://water.epa.gov/drink/
contaminants/basicinformation/nitrate.cfm; Ferrier and Jenkins, 2010; Kolpin et al., 1999]. In 5101 wells
sampled throughout the continental U.S., 20% of wells in the agricultural land use setting had NO3-N
concentrations higher than the MCL, while 3% of wells in the urban land use setting and 4% of wells in
major aquifers exceeded the MCL [Burow et al., 2010]. Madison and Burnett [1985] have suggested a value

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of 3 mg L 1 as a possible division between natural and anthropogenic (human-related) sources of NO3-N in

groundwater.
The fate and transport of NO3-N in groundwater have been very well studied over the world [e.g., Burow et al.,
2010; DeSimone, 2009; Lin et al., 2007; Noland and Stoner, 2000; Adamski and Pugh, 1996; Wilkinson and Maley,
1996; Mueller et al., 1995; Kolpin et al., 1994; Wilkinson and Maley, 1994; Ziegler et al., 1994; Sievers and Fulhage,
1992; Mesko and Carlson, 1988; Madison and Burnett, 1985]. However, our understanding of the processes or
factors controlling NO3-N concentrations in groundwater of claypan soil areas is lacking. Claypan soils cover
about 41,000 km2 of Illinois, Indiana, Kansas, Missouri, Ohio, and Oklahoma [Pomes et al., 1998; Lerch et al.,
2008]. The smectitic mineralogy of the claypan and subsoil horizons results in restricted downward movement
of air and water, slows root development, and promotes surface water runoff [Hjelmfelt et al., 1999; Blanchard
and Donald, 1997; Blevins et al., 1996; Jamison et al., 1968]. However, a number of studies conducted over the
last two decades in Goodwater Creek Experimental Watershed (GCEW) in Missouri have indicated that NO3-N
leaching to shallow groundwater aquifers has occurred in the claypan soils. [Donald et al., 1998; Kelly and
Pomes, 1998; Wilkinson et al., 2000]. Groundwater in GCEW is much more vulnerable to contamination by
NO3-N than by common soil-applied herbicides [Blanchard and Donald, 1997; Pomes et al., 1998; Wilkinson
et al., 2000; Lerch et al., 2005]. Despite all the efforts to establish an effective management system that can
protect water quality in GCEW, more than 25% of the groundwater wells in the watershed had NO3-N concentrations greater than the MCL [Kitchen et al., 1997]. In 2006 and 2007, there were serious taste and odor
problems for the water in the Mark Twain Lake (receiving water body for most of the Salt River Basin) due
to excess nutrient loading [Arabi et al., 2012].
Even though water quality has been very well studied at GCEW as discussed above, these studies have not
investigated the factors or specic processes (e.g., land uses, topography, soils, climate, crops, hydrologic
pathways, chemical mixing, and hydrogeologic characteristics) affecting watershed vulnerability to NO3-N
transport. These studies either did not encompass an area with enough variation in these factors or covered
such a large area that the variability in climate, soil mineralization potential, types of soils and crops, and sample
collection timing (e.g., limited to short periods) masked the impact of these factors. Our study reported here
was aimed at understanding the susceptibility of groundwater in claypan watershed to nitrogen-fertilizer
applications and the processes or factors that control NO3-N concentrations in groundwater within GCEW.
Specically, the objectives of this study were to (1) inspect the spatial and temporal variations of NO3-N concentrations in GCEWs groundwater, particularly with well depth at scales ranging from individual well, well nest,
and eld to the entire watershed during the period 1991 to 2004; (2) understand the processes or factors that
control the spatial and temporal variability of NO3-N concentrations in GCEWs groundwater; and (3) evaluate
NO3-N concentrations in groundwater at GCEW by comparing with other agricultural watersheds throughout
the continental United States.

2. Study Area
GCEW is located in the central claypan Major Land Resource Area 113an area of about 30,000 km2in
Audrain and northeast Boone Counties, about 45 km north of Columbia, in north-central Missouri (Figure 1).
The watershed covers 77 km2 and is a subwatershed to Youngs Creek within the larger Long Branch watershed
of the Salt River, draining to Mark Twain Lake, a major public water supply and recreation area. The study area
has signicant heterogeneity in soils, hydrology, and land uses (intensive row-cropping) [Blanchard and Lerch,
2000; Lerch et al., 2008]. The watersheds topography is characterized by broad, nearly at divides, gentle side
slopes (03%)elevation from the divide to the outlet ranges between 235 and 271 m above sea level (asl)
(Figure 1)and broad alluvial valleys often dissected with small streams [Alberts et al., 2003].
The long-term water-budget analyses (from 1948 to 2003) of the GCEW indicate that the mean annual precipitation was about 997 mm [Alberts, 2003; Arabi et al., 2012], of which 18%, 36%, 28%, and 18% occurred
between JanuaryMarch, AprilJune, JulySeptember, and OctoberDecember periods, respectively.
Spring rainfall (May to June) during seedbed preparation and planting is short, but intense [Alberts et al.,
2003; Arabi et al., 2012]. Fall rainfall often occurs as low intensity, long-duration events due to slow moving
cold fronts [Alberts et al., 2003]. Mean annual streamow was 292 mm, which is about 30% of mean annual
precipitation [Alberts et al., 2003; Arabi et al., 2012], whereas evapotranspiration accounted for about 70%
of the mean annual precipitation [Alberts et al., 2003]. Baseow accounted for about 15% of streamow

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Figure 1. (top) Maps showing the location and boundary of Goodwater Creek Experimental Watershed (GCEW) in Audrain
and Boone Counties, MO, elevations (meters asl), and the locations of groundwater wells, weather stations, rain gauges, and
streamow gauges in the watershed (modied after Blanchard and Donald [1997]). (bottom) Maps showing the locations of
well nests and elds (I) and the arrangement of well nests in well elds (II to VI), along with elevation contours (meters asl)
and soil series.

discharge, and surface runoff accounted for about 85% [Alberts et al., 2003; Arabi et al., 2012]. Maximum and
minimum daily mean temperatures were 17.1 and 6.3C [Alberts et al., 2003; Arabi et al., 2012].
The land uses in this watershed include (a) row crops with an area of about 54 km2, 6978% of the watershed
area; (b) pasture and other grassland (10.4 km2, 1217%); (c) woodland (4.5 km2, 6%); and (d) a small town at
the upper end of the watershed (3.3 km2, 4%) [Arabi et al., 2012; Baffaut et al., 2009]. The predominant crops in
the watershed follow the ranking of soybeans corn = hay > wheat > sorghum, and the typical crop rotations are
corn/soybeans, corn/soybeans/wheat, soybean/soybeans/wheat, and sorghum/soybean/wheat [Alberts et al.,
2003]. Historical agriculture applications in the Goodwater Creek Experimental Watershed are shown in Table 1.
Quaternary stratigraphy for north-central Missouri was adapted for the GCEW based on core samples
collected in previous studies [Blanchard and Donald, 1997; Sharp, 1984; Guccione, 1983]. Figure 2 presents

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Table 1. Historical Land Uses and Fertilizer Applications Over the Three Farm Fields in the GCEW
Cropping History
Location

Manure Applications

Applied Nitrogen (kg/ha)

19301960

19601980

19801990

19902004

19301960

19601980

19801990

19902003

Field 1

Cultivated-unsure
of crops

42% Corn
50% Soybean
8% Sorghum
50% Soybean
50% Sorghum

Few animal
manure

No animal
manure

Total (13 years) = 1250

Annual mean = 96

Cultivated-unsure
of crops

Few animal
manure

Few animal
manure

No animal
manure

Total (11 years) = 749

Annual Mean = 68

Field 3

70% Corn
20% Oats
10% Wheat

40% Soybean
20% Wheat
40% Sorghum
50% Soybean
40% Wheat
10% Sorghum
50% Soybean
50% Wheat

No animal
manure

Field 2

10% Corn
85% Soybean
5% Sorghum
20% Corn
40% Soybean
40% Wheat
50% Corn
30% Soybean
20% Wheat

Animal
manure

19601965
Animal manure
19651975 No
animal manure

19751982
Animal manure
19821990 No
animal manure

Total (11 years) = 890

35% Corn
35% Soybean
30% Wheat

Annual mean = 81

Arabi et al. [2012], Baffaut et al. [2009], Lerch et al. [2005], Ghidey et al. [1997], and Kitchen et al. [1997].

a modied version of the strata based on current studies of Brooks and Saia [2012] and Pagan [2009], which
shows that the total thickness of the till strata is around 16 m at the summit landscape position. The till is
especially vulnerable to soil erosion, which has degraded the upper or lower soil units at some locations
throughout the basin [Arabi et al., 2012]. Wisconsin and Illinoian loess deposits are separated by a claypan
layer, and the three layers that overlie the till are about 3 m thick at the summit position and are thin or absent
near streams. At most locations, a paleosol in till is present between the upper glacial till unit and Illinoian loess,
at the bottom of the lower till unit, and separating the two pre-Illinoian glacial till units. The glacial till overlies
Pennsylvanian shale and Mississippian limestone, and in some locations preglacial sediments including peat.
Alluvial deposits are present near streams, particularly near the outlet of the watershed, where the loess, till,
and Pennsylvanian deposits have been completely eroded and alluvium directly overlies the Mississippian

Figure 2. (top) Sketch of generalized cross-section and stratigraphy of geological deposits in GCEW (modied after Pagan [2009], Blanchard and Donald [1997], and Guccione
[1983]). (bottom) Variation of accumulative fraction of clay, sand, and silt contents with depth from drilled cores at selected nests (e.g., F1-C means well nest C in Field 1). Note
that the darker shaded areas near the bottom mark the depths that were screened and the last four proles show fractions averaged to eld and watershed scales.

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Burlington Limestone [Alberts et al., 1995; Blanchard and Donald, 1997]. The loess and glacial till have sufcient
water yield for domestic use and together will be referred to as the glacial aquifer.
Soils within GCEW are distinguished by the presence of a naturally formed argillic horizon (claypan layer
about 0.15 to 0.45 m thick) located 0.130.37 m below the soil surface [Anderson, 2011; Jamison et al.,
1968]. The clay content ranges from 350 to 600 g/kg [Blanco-Canqui et al., 2002]. The clay contents of the
argillic horizon is generally greater than 50%, and consisting of 38%, 34%, 21%, and 7%, respectively, of
montmorillonite, quartz, kaolinite, and illite [Blanco-Canqui et al., 2002]. The claypan soils are predominantly
classied as hydrologic soil groups C and D [Arabi et al., 2012], which have moderately to high surface runoff
potential when thoroughly wet [U.S. Department of Agriculture, 2003]. Table 2 shows the spatial distribution of
some hydraulic conductivity and effective porosity over eld and entire watershed scales in GCEW.

3. Methods
3.1. Distribution of Wells and Information on Well Drill Cuttings
Ninety-six groundwater wellsranging in depth from 2.7 to 15.7 m with a screened interval of 0.61 and 1.2 m
for shallow and deep wells, respectivelyare distributed in three farm elds and other locations throughout
the watershed at GCEW. In three farm elds (Fields 13), the monitoring wells were organized by ve- to
eight-well nests (e.g., A, B, C, D, and E in Figure 1 and Table 3). The number of wells for each nest ranges from
1 to 5 and the wells within a nest are within about 25 m2 of each other (Table 3 and Figure 1). All monitoring
wells were furnished by 5.08 cm diameter polyvinyl chloride pipes and equipped with water pumps. Twentyfour production wells located throughout the watershed (watershed wells) were also sampled.
Soil extracts were obtained from core cutting samples by the University of Missouri-Columbia Soil Characterization
Laboratory during the drilling of the deepest wells at Field 1 (nests C, D, and E), Field 2 (nests A and C), and Field 3
(nests A, B, C, D, and E). These extracts were collected with a 1.6 m long, 7.62 cm diameter core barrel, which had
a removable acetate liner [Kitchen et al., 1997]. Drill cutting samples were divided horizontally according to soil
horizons or visible textural or color changes. Where the core appeared uniform in texture and color, it was
divided into 30 cm increments [Kitchen et al., 1997]. Soil samples were divided into two subsamples, one of
which was oven dried to determine water content, and the other to obtain soil texture (Figure 2).
3.2. Water Quality Data
The water quality data of rainfall, stream water, and groundwater was obtained from U.S. Department of
Agriculture Agricultural Research Service (USDA-ARSs) Cropping Systems and Water Quality Research Unit
(CSWQRU) through Sustaining the Earths Watersheds, Agricultural Research Data System [Sustaining the
Earths Watersheds, Agricultural Research Data System, 2013, http://www.nrrig.mwa.ars.usda.gov/stewards/
stewards.html]. Groundwater wells were sampled quarterly (March, June, September, and December) from
1991 through 1996, and semiannually (March and September) from 1997 through 2004. Because of low
recharge rates, some deeper wells were only sampled annually. Prior to sample collection, three volumes
of water were purged out from each well. Samples were collected in 900 mL amber glass bottles, placed in
a cooler, and transported to the laboratory at CSWQRU in Columbia, MO, at the end of the day. Additional
details of well installation and sample collection procedures were previously documented [Blanchard and
Donald, 1997; Kitchen et al., 1997]. Stream water was sampled (through concrete V notch weirs) weekly during
the growing season and every 2 weeks in winter. Precipitation was sampled after each storm event from rain
gages installed over the watershed. From April 1991 to September 2004, 2583, 4572, and 442 samples were
collected from groundwater, stream water, and rainfall, respectively. Water samples were ltered through
0.45 m nylon lters within 48 h of sampling. Samples were preserved by lowering pH to approximately
2.0 using sulfuric acid and refrigerated prior to analysis. Samples were analyzed for NO3-N within 5 days if
applicable, and if not, they were frozen and the analysis was done within 30 days of collection [Blanchard
and Donald, 1997; Kitchen et al., 1997]. Nitrate-N analyses were determined colorimetrically using a Lachat
ow injection system (Lachat Instruments, Milwaukee, Wisconsin), and the detection limit (DL) for this
method was 0.05 mg L 1.
3.3. Statistical Analysis
The Kruskal-Wallis analysis of variance by ranks and median test (H test) is a nonparametric method (does not
assume a normal distribution of the data or equal number of observations of treatments) for testing whether

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Table 2. Spatial Distribution of Hydraulic Conductivity and Effective Porosity, as Well as the Number of Wells in Each Depth Over Field and Entire Watershed Scales
Field 1
Stratum Series
Top of claypan Wisconsin loess
Within claypan Wisconsin loess
Base of claypan Wisconsin loess
Illinoian loess
Paleosol in till
Glacial till
Paleosol in till
Glacial till
Pennsylvanian shale

Depth Range (m)

0.00.46
0.460.71
0.711.1
1.12.85
2.853.24
3.248.5
8.510
1013
1315.2

a
Blanco-Canqui et al. [2002]: Ksat = 72 mm/h
b
Kelly and Pomes [1998].
c
Blanchard and Donald [1997].
d

Hydraulic Conductivity K (m/s)

b

1.68 10
1.98 10
b
9.87 10
c,d
5.0 10
b,c,d
5.0 10
c,d
4.5 10
c,d
5.0 10
c,d
4.5 10
c,d
1.9 10

7
7
7
6
7
6
8

Field 2

Field 3

Watershed Wells

Watershed GCEW

ne

NW

ne

NW

ne

NW

ne

NW

ne

NW

48
47
43
40
38
35
30
34
31

0
0
0
5
0
11
3
34
31

47
44
40
38
41
36
27
32
-

0
0
0
1
0
15
1
3
-

46
41
39
36
40
33
27
32
35

0
0
0
5
2
14
2
3
1

52
48
43
-

0
0
0
3
0
19
2
0
0

48
44
41
38
39
35
28
33
32

0
0
0
14
2
59
8
9
4

in the depth (00.46 m). ne: effective porosity; NW: number of wells.

Sharp [1984].

samples originate from the same distribution. As the data presented in this study were likely not normally
distributed, Kruskal-Wallis approach was used to conduct an analysis of variance on the ranked data to examine the signicance of the spatial and temporal variations of median NO3-N concentrations using software
developed by StatSoft Inc. (19842010). The a priori level of signicance () was chosen to be 0.05 for all
statistical analyses.
Spearmans rank order correlation (S-R) was used to obtain the correlation coefcients. Spearmans rank is a
nonparametric correlation, where chi-square statistic computed for two-way frequency tables, and provides a
careful measure of a relation between the two (tabulated) variables. Moreover, Spearmans rank assumes that
the variables under consideration were measured on at least an ordinal (rank order) scale, that the individual
observations can be ranked into two-ordered series [Siegel and Castellan, 1988]. The Spearmans rank order
correlations (S-R) were considered to be positively and perfect positive correlated if its value >0.1 and 1,
respectively, and negatively and perfect negative correlated if its value < 0.1 and 1, respectively
[Siegel and Castellan, 1988].

4. Results
4.1. Nitrate-N Concentrations in Groundwater, Stream Water, and Precipitation
Within GCEW, median nitrate-N concentrations were in the order groundwater > stream water > precipitation (Table 4 and Figure 3). The nitrate-N concentrations in groundwater for the entire watershed varied from
DL to 46.0 mg L 1, with a median of 7.8 mg L 1. About 29% of the 2583 groundwater samples (38% of the 96
wells) had NO3-N concentrations greater than the MCL. The nitrate-N concentrations in stream water ranged from DL to 145.0 mg L 1 with a median of 1.3 mg L 1. About 7% of the 4572 stream water samples
exceeded the MCL. The nitrate-N concentrations in rainwater were lower than 6.0 mg L 1 with a median
of 0.3 mg L 1. About 99.8% of the 442 samples had NO3-N concentrations varying between 0.05
and 3.0 mg L 1.
4.2. Spatial Variation of Nitrate-N Concentrations in Groundwater
The median nitrate-N concentrations in groundwater over well nests and elds (Figure 3 and Table 4) were
also used to examine the spatial variation. Results of the H test indicated that the median NO3-N concentrations were signicantly different at all scales within and among nests, elds, and the watershed
(p < 0.001). The median NO3-N concentrations were also signicantly different over individual wells except
for wells in nest B of Field 1, nests C and G of Field 3, and nest E of watershed wells.
The nitrate-N concentrations in wells of Field 1 varied between 0.3 and 46.0 mg L 1 with a median of
4.6 mg L 1 (Table 4). Nest A had the greatest median concentration among all nests in Field 1 (Figure 3).
About 7% of the 589 samples collected from Field 1 (about 20% of the 25 wells) had NO3-N concentrations
>10 mg L 1, with the majority of those wells from nests A, D, and E. In Field 2, the nitrate-N concentrations
varied between 0.1 and 11.7 mg L 1, a much narrower range than in Field 1, with a median of 8.9 mg L 1.

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Table 3. Hydrologic, Soil, and Topographic Characteristics of the Areas Occupied by Wells Organized by Fields and Nests
Soil Type Distributions
Field ID
Field 1

Field 2

Field 3

Watershed
wells

Nest
ID

No. of
Wells

1A
1B
1C
1D
1E
2A
2B
2E
2C
2D

5
5
5
5
5
5
3
4
4
4

3A
3E
3H
3B
3C
3D
3F
3G
0A
0B
0C
0D
0E
0F
0G
0H

5
5
4
3
4
2
3
1
4
3
2
4
2
2
3
4

Latitude

Longitude

39.2259079
92.1171863
39.2274985
92.1173205
39.2312061
92.1194111
39.2319456
92.1188754
39.2328156
92.1183258
39.2530602
92.1238151
39.2530003
92.1247928
39.2518823
92.1238273
39.2525977
92.1256610
39.2518819
92.1229436
Area Not Occupied With Wells
39.2323376
92.1490584
39.2312136
92.1502471
39.2304786
92.1489512
39.2304760
92.1471665
39.2305235
92.1520808
39.2310289
92.1523987
39.2305979
92.1534198
39.2307563
92.1533490
39.2553900
92.1506538
39.2552315
92.1451503
39.2551066
92.1397131
39.2551785
92.1268072
39.2681910
92.1183250
39.2827462
92.0789218
39.2833124
92.0813832
39.2827267
92.0843113

Elevation Well Depth

(m)
Range (m)
265.5
264.6
263.7
263.5
262.7
262.4
262.1
262.7
261.5
263.1

2.713.4
2.714.5
2.714.2
2.711.5
2.79.7
2.712.1
3.56.5
4.810.3
3.58.3
6.710.6

262.4
260.9
262.1
263.7
259.4
259.1
259.1
259.1
261.2
260.3
253.6
260.9
255.7
248.7
251.8
254.8

6.511.7
2.79.9
2.7
8.014.0
3.08.5
3.46.6
3.05.0
2.87.4
4.110.0
6.010.0
2.24.1
3.75-10.3
2.29-4.13
2.34.2
3.47.2
3.88.4

Soil
Series

Adco
Adco
Adco
Mexico
Mexico
Mexico
Mexico
Mexico
Leonard
Putnam
Adco
Mexico
Mexico
Mexico
Adco
Leonard
Vesser
Vesser
Vesser

Percent of
Area %

Slope
Percent

a,b

Area
2
(km )

Drift
Thickness (m)

Hydraulic
Gradient

0.355

16

0.004

0.242

13

0.006

0.204

15

0.009

70

02

30

13

30

13

25
15
30

14
01
02

65

13

10
15

02
14

10

01

NA

NA

NA

0.12

11

0.008

NA

NA

NA

0.1

11

0.01

a
Blanchard
b

and Donald [1997];

Sharp [1984].

About only 1% of the 433 samples collected from Field 2 (10% of the 20 wells) had NO3-N concentrations
>10 mg L 1, mainly from wells in nest D. In Field 3, the nitrate-N concentrations varied from DL to
26.4 mg L 1, with a median of 11.4 mg L 1. About 58% of the 969 samples collected from Field 3 (82% of
the 27 wells) had NO3-N concentrations >10 mg L 1, with nests A, B, and F having the most wells with high
concentrations. In watershed wells, about 24% of the 592 samples collected from these locations (67% of 24
wells) had NO3-N concentrations >10 mg L 1, with a range from DL to 26 mg L 1, and a median of
6.5 mg L 1. Nitrate-N concentrations were highest in Field 3 (Figure 3). Also, nitrate-N concentrations that
exceed the MCL in Field 3 represent the greatest percentage among all the elds (Table 4).
4.3. Variations of Nitrate-N Concentrations in Groundwater With Well Depth
The relationship between NO3-N concentrations and well depths at entire watershed scale (Figure 4)
indicates that the median nitrate-N concentrations were high near the surface (~8 mg L 1), decreased from
near surface to about 3.5 m below the surface (to ~4.5 mg L 1), increased with depth below 3.5 m to peak
concentrations between 8.5 and 10 m (~12 mg L 1) and then decreased signicantly with depth below
10 m (<2 mg L 1) (p < 0.001). The median NO3-N concentrations over depth at individual eld scale of
Fields 1, 2, and 3 followed, in general, the similar pattern as for the entire watershed, with peak values
occurring at slightly different depths (Figures 5 and 6). Moreover, the same trend was also seen at nest scale,
including nest A in Fields 1, 2, and 3 and nest B in Field 3 (Figure 5). But the trend did not hold for nests B and
C in Field 1, with a monotonic decreasing trend with well depth.
Even though the variations of NO3-N concentrations in some well nests did not follow the bulge-like pattern,
interestingly, there was a similar pattern across different elds such as nests D and E of Field 1 with nests
C and E of Field 2, where NO3-N concentrations increased with depth (Figure 5). Furthermore, within some nests
shallow wells had the greatest NO3-N concentrations (e.g., nest C in Field 1 and nest G in Field 3).
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Table 4. Descriptive Statistics of the Nitrate-N Concentrations in Groundwater, Stream Water, and Rainfall at GCEW
NO3-N Concentrations (mg L
1991 to 2004
Site Identier

No. of Samples

No. of Wells

Median

GCEW
Field 1
Nest_1A
Nest_1B
Nest_1C
Nest_1D
Nest_1E
Field 2
Nest_2A
Nest_2B
Nest_2C
Nest_2D
Nest_2E
Field 3
Nest_3A
Nest_3B
Nest_3C
Nest_3D
Nest_3E
Nest_3F
Nest_3G
Nest_3H
Watershed wells
Nest_0A
Nest_0B
Nest_0C
Nest_0D
Nest_0E
Nest_0F
Nest_0G
Nest_0H

2583
589
129
104
110
119
127
433
92
64
98
84
95
969
120
298
95
85
99
114
137
21
592
104
69
83
92
41
49
67
87

96
25
5
5
5
5
5
20
5
3
4
4
4
27
5
5
4
3
4
2
3
1
24
4
3
2
4
2
2
3
4

6.9
4.6
7.4
1.3
3.4
4.7
6.2
8.9
1.8
3.0
3.5
6.8
7.7
11.4
15.3
13.5
12.5
8.0
10.3
12.7
11.5
9.8
6.5
19.2
12.2
0.2
7.4
0.1
4.2
6.2
1.5

GCEW

4572

1.3

GCEW

442

0.3

) from

Range
Groundwater
<0.0546
0.346
2.212.9
0.36
0.446
1.69.9
210.6
0.111.7
0.14.5
1.27.0
1.55.4
4.711.7
1.39.2
<0.0526.4
1.822.1
<0.0526.4
<0.0519.7
1.312.6
<0.0511.8
6.917.3
<0.0515.7
7.510.6
<0.0525.8
0.425.8
8.315.6
<0.052.2
312.2
<0.050.4
0.38.5
1.98.0
0.36.1
Stream water
<0.05145
Rainfall
<0.16

% of Sample with NO3-N

1
Concentration (mg L )

% of Wells With NO3-N

1
Concentration (mg L )

>0.05

>3

>10

>10

93
100
100
100
100
100
100
100
100
100
100
100
100
81
100
90
81
100
84
98
84
100
86
100
100
41
100
20
98
100
100

74
70
86
4.8
57
97
93
67
43
50
76
100
99
77
99
81
77
89
81
98
83
100
64
91
100
0
100
0
74
93
30

29
7
17
0
6
0
8
1
0
0
0
6
0
51
71
61
54
21
47
87
58
33
24
75
93
0
2
0
0
0
0

38
20
60
0
20
0
20
10
0
0
0
50
0
78
80
80
75
67
75
100
67
100
33
75
100
0
50
0
0
0
0

99

21

99.8

0.002

4.4. Temporal Variation of Nitrate-N Concentrations in Groundwater

Temporal variation of the median NO3-N concentrations over the well depth at nest scale did not change
signicantly over seasons for all well nests (p > 0.05) (Figure 6). The temporal variation of the annual median
NO3-N concentrations did not show any evident trend at the watershed scale from 1991 to 2004 (p > 0.05,
Spearmans correlation coefcient (S-R) = 0.07) (Figure 7). Annual median NO3-N concentrations have significantly increased since early 1990s in the watershed wells (p < 0.05, S-R > 0.1), but signicantly decreased at
Field 3 (p < 0.05, S-R < 0.1). There was no signicant trend for Fields 1 and 2 (p > 0.05, 0.1 < S-R < 0.1). At
the nest scale, median NO3-N concentrations have signicantly increased in nests C, D, and E of Field 1; A, B,
and E of Field 2; and A, C, D, and H of watershed wells (p < 0.05, S-R > 0.1), but signicantly decreased in nests
C of Field 1; C and D of Field 2; A, B, C, D, F, G, and H of Field 3; and B and G of watershed wells (p < 0.05,
S-R < 0.1). Moreover, nests A and B of Field 1, E of Field 3, and nests E and F of watershed wells (p > 0.05,
0.1 < S-R < 0.1) showed no signicant trends.

5. Discussion
5.1. Susceptibility of Groundwater in GCEW to Nitrogen-Fertilizer Applications
Claypans impede the downward movement of water and reduce the rate of water inltration [Blevins et al.,
1996; Hjelmfelt et al., 1999; Blanchard and Donald, 1997], causing lateral movement of soil water that results

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in a high degree of vulnerability to

surface water transport of nutrients,
sediment, and herbicides [Lerch and
Blanchard, 2003; Arabi et al., 2012;
Blanco-Canqui et al., 2002]. However,
comparing the results of NO3-N concentrations in groundwater at GCEW with
those in agricultural watersheds of
other studies conducted at national,
state, and regional scales indicates that
the median NO3-N concentrations and
the percentage of wells with NO3-N concentrations >10 mg L 1 in this claypan
watershed were much higher than the
other watersheds (Table 5), suggesting
that the claypan-dominated watershed
is surprisingly susceptible to nitrate-N
leaching.

Figure 3. Variation of median nitrate-N concentrations in (a) precipitation,

stream water, and groundwater (GW) over elds and entire watershed,
and (b) groundwater median nitrate-N concentrations distributed over
nests. The numbers above whisker boxes are the number of samples.

The claypan layer obviously does not substantially limit the leaching of NO3-N into
the groundwater system. Water content
of the plant root zone decreases during
summer because evapotranspiration
from rapidly growing and maturing crops
exceeds rainfall amount, resulting in signicant cracks and macropores in the
claypan layer [Alberts et al., 2003; Donald
et al., 1998; Baer and Anderson, 1997].
The occurrence of the cracks and its geometry (depth and volume) in the claypan
layer depends on many factors, including
weather, topography, vegetation, claypan
structure, the distance from ground

Figure 4. Distribution of median nitrate-N concentrations in groundwater with well depths for (a) median values of the
entire period for all 96 individual wells (red, dashed lines mark the data range and where maximum nitrate-N concentration occurred) and (b) median values of the wells within 1 m depth interval for the whole watershed, median box values are
median percentiles, and median whisker values are 5% condence interval. TN means total number of samples, and N
beside each box is the number of samples in that depth.

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surface to the claypan, and the thickness

of the claypan layer [Arnold et al., 2005;
Baer and Anderson, 1995, 1997; White
and Gartner, 1981]. The depth of such
cracks could vary from a few millimeters
(micropathways) to greater than 1 m
[Anderson, 2011]. These cracks can create
preferential pathways for groundwater
recharge through the claypan layer. In
addition, groundwater recharge to the
alluvial aquifer may be from stream water
inltration and bank storage following
high discharge periods [Blanchard and
Lerch, 2000]. Overall, nitrate-N appears
to be transported via preferential pathways that extend from the soil surface
through the claypan and into the glacial
aquifer, a transport mechanism for contaminants in claypan watershed that is
consistent with previous studies [e.g.,
Kelly and Pomes, 1998; Wilkinson et al.,
2000; Donald et al., 1998; and Flury et al.,
1994; Pagan, 2009].
Also, nitrate-N concentrations in groundwater were signicantly higher than
stream water at GCEW (Figure 3), indicatFigure 5. Distribution of median nitrate-N concentrations in groundwater ing that less dilution of NO3-N occurred in
the groundwater and that nitrication in
with well depths at (top) well nest scale (e.g., in F1-nests, each curve
represents a nest labeled by a capital letter in the legend and each data
the shallow subsoil likely converted
point represents the median value of the individual wells in that nest at
ammonium-N (from applied fertilizers
that depth for the entire observation period) and (bottom) eld scales,
and/or mineralization of organic matter)
where each data point represents the median value of all individual wells
to nitrate by soil microbes [Kitchen
within the same depth in that eld.
et al., 1997]. The cracks and macropores
in the claypan layer bring about elevated dissolved oxygen concentrations along groundwater pathways, as measured by Wilkinson et al.
[2000] in a claypan watershed, which results in nitrication as observed by Pomes et al. [1998]. Other evidence
to support nitrication was that none of 96 wells in the watershed was artesian, suggesting that the pressure
at water table is at equilibrium with atmospheric pressure and air is accessible to the groundwater system, at
least to the upper part of the aquifer.
5.2. Controls on Spatial and Temporal Variations of Nitrate-N Concentrations in Groundwater
Nitrate-N concentrations in groundwater at GCEW signicantly varied spatially across elds (Figure 3). The
spatial variation is deemed to be primarily controlled by the history of fertilizer uses and variable materials
consisting of the aquifer. The median NO3-N concentrations were greatest in Field 3 among all elds
(Table 4 and Figure 3b), which is consistent with earlier data published previously for the same watershed
[e.g., Kitchen et al., 1997; Arabi et al., 2012; Baffaut et al., 2009; Lerch et al., 2005; Ghidey et al., 1997]. Field 3
has been more intensively farmed than Fields 1 and 2 since 1930s (Table 1). Manure was the primary fertilizer
applied from 1930 to 1990 in Field 3 but rarely used in Fields 1 and 2 during the same period. Inorganic fertilizers were used after 1990 in all elds. Even though more inorganic fertilizers were applied in Field 1 than
Field 3 after 1990, it is deemed that the earlier, continuous use of manure was the primary reason for the
higher NO3-N concentrations in groundwater at Field 3. Along with the very low hydraulic conductivity of
the aquifer (Table 2) when compared with nonclaypan watersheds of Saxton and Rawls [2005] and Blevins
et al. [1996], it is suggested that nitrogen from historical manure still persists in the current groundwater

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Figure 6. Seasonal variation of the median nitrate-N concentrations in groundwater with depth at the well nest scale (e.g.,
in F1-A wells, each curve represents a season and each data point represents the median value of the observation period for
that season at the individual wells in nest A and Field 1).

system at GCEW. Particularly, the effective porosity is lower at Field 3 than at Fields 1 and 2 (Table 2) and Field 3
has greater clay content than Fields 1 and 2 (Figure 2). It is likely that overall hydraulic conductivity is lower at
Field 3 than at Fields 1 and 2, resulting in greater retention of past NO3-N.
The temporal variation of annual median NO3-N concentrations did not show any evident trend from 1991 to
2004 at the watershed scale (Figure 7). At the eld scale, there was not a signicant trend for Field 1 and Field 2
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Figure 7. Spatial and temporal variations of median nitrate-N concentrations in each nest, eld, and the entire watershed during the period of 19912004. Note, for
example, that F1-A means well nest A in Field 1, WW means watershed wells, also the last panel at each row represents the median value for that eld (e.g., F1, F2, F3,
and watershed wells), and the large one at top right is for the median value of the entire watershed. S-R represents Spearmans correlation coefcients of the
nonparametric trend lines over time, and p represents the a priori level of signicance. Values (in bold) that lie in the range 0.1 < S-R < 0.1 or p < 0.05 are
signicantly correlated.

either. However, NO3-N concentrations tended to decrease in Field 3, particularly from 1991 to 2000. The
declining trend of NO3-N concentrations in Field 3 suggests that the storage of old NO3-N accumulated since
1930s has been diminishing and gradually recharged by recent groundwater with relatively lower NO3-N
concentrations due to the lower N fertilizer inputs at this site since 1991.
5.3. Controls on Nitrate-N Concentrations in Groundwater Over Aquifer Strata
The bulge-like prole of NO3-N concentrations over depth is deemed to be primarily caused by the vertical
distribution of hydraulic conductivity associated with the strata of the geological deposits. Hydraulic conductivity (K) is about 2 10 6 m s 1 in the topsoils above the base of claypan (00.71 m below the land surface). It
decreases by nearly an order of magnitude from the base of claypan through Illinoian loess (1.12.85 m) and
Paleosol in till (2.853.24 m) (Table 2). The K value increases to 4.5 10 6 m s 1 in glacial till from 3.24 to 8.5 m
and then lowers to 5 10 7 m s 1 in Paleosol in till from 8.5 to 10 m. The K value increases again when glacial
till reappears (1013 m) before it reaches lowest value in the stratum dominated by Pennsylvanian shale
(1315.2 m). The Paleosol stratum from 8.5 to 10 m (the second Paleosol stratum below the land surface)
is much thicker than the rst one from 2.85 to 3.24 m and has lower effective porosity than any other strata.
Unlike the claypan layer just below the topsoil, which has cracks and extensive macropores, the second
Paleosol stratum is apparently relatively impermeable at some well locations. The signicant decrease of
hydraulic conductivity and porosity (Table 2) in the second Paleosol stratum plays a major role in controlling the distribution of NO3-N concentrations with depth, resulting in the bulge-like concentration pattern
(Figure 4). Based on Darcys law, the signicant reduction of hydraulic conductivity in the second Paleosol
stratum resulted in faster lateral ow in the glacial till above the Paleosol than vertical inltration into it. As
a result, more old water was retained in the second Paleosol layer than layers above it. The old water from
1930s to 1990s apparently contained higher NO3-N concentrations than recent water due to higher N
inputs from manure and/or fertilizer applications during this period, particularly in Field 3 (Table 1). No data
of NO3-N concentrations in groundwater are available for the period before 1990s, but NO3-N concentrations
in groundwater have decreased in Field 3 since 1991 (Figure 7), suggesting that NO3-N concentrations in
older groundwater were higher. All of these factors together result in highest NO3-N concentrations in
groundwater in the second Paleosol layer.
In addition, the second Paleosol layer limits oxygen ux into the strata below it and creates an anaerobic
environment for the lower strata. This process facilitates denitrication in the lower strata and resulted in

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Table 5. Summary of Nitrate-N Concentrations in Groundwater in Agricultural Watersheds by Study Areas Throughout the U.S.
Study
USA
b,c,d,e
USGS-NAWQA
Mid-continental US
f,g,h
USGS-Reconnaissance
e,f,g,h,I,j,k,l,m
Missouri

Whole Watershed
Three eld study

Field 1, single eld study

Field 2, single eld study

Field 3, single eld study

Sampling
Period

No. of Wells
Analyzed

NO3-N
1
(mg L )

% of Wells With NO3-N

1
0.05 (mg L )

% of Wells With
1
NO3-N 3 (mg L )

% of Wells With NO3-N

1
>10 (mg L )

Range of NO3-N
1
(mg L )

19912004
19921995
19701992
1991

2205
926
2012
303

3.1 (M)
3.4 (M)
3.4 (M)
0.2 (M)

63

29

23
19
21
13

0.0216
<0.0536

1992
19701992
19901991
1991
19881989
19871989
19861987

147
29
123
159
95
201
124

2 (M)
0.8 (M)
-

28
41
46
61
22
43
-

19
34
20
24
13
22
17.5

<0.05 to 50
-

2004
1991
2004
19912004
19911995
1991
2004
19912004
19912003
1993
1991
2004
19912004
1991
2004
19912004
1991

86
78
65
72
72
54
25
25
25
25
20
20
20
18
20
27
16

4 (M)
1 (M)
5 (M)
6 (A)
7 (A)
7 (A)
6 (A)
5 (A)
5 (A)
5 (A)
4 (A)
4 (A)
4 (A)
5 (A)
8 (M)
9 (A)
12 (A)

24
25
7
-

<0.05 to 30
<0.05 to 30
<0.05 to 15
<0.05 to 24
<0.05 to 13
<0.05 to 46
<2 to 8
<2 to 12
<0.05 to 16
<0.05 to 24

54
78
89
45
77
n,o,p,q
Missouri-GCEW
-

M: median; A: average; NAWQA: national water-quality assessment; Midcontinental U.S. (Midwestern U.S.): Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota,
Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin.
b
DeSimone [2009].
c
Burow et al. [2010].
d
Noland and Stoner [2000].
e
Mueller et al. [1995].
f
Kolpin et al. [1994].
g
Madison and Burnett [1985].
h
Wilkinson and Maley [1996].
i
Sievers and Fulhage [1992].
j
Ziegler et al. [1993].
k
Ziegler et al. [1994].
l
Mesko and Carlson [1988].
m
Adamski and Pugh [1996].
n
Kitchen et al. [1997].
o
Lerch et al. [2005].
p
Blanchard and Donald [1997].
q
Kitchen et al. (in press).

the observed decreases in nitrate concentrations below the second Paleosol and was consistent with observations by Korom [1992] and Kolpin et al. [1994] for claypan watersheds. Even though nitrication appears to
dominate over denitrication for the aquifer as a whole as discussed in 5.1, denitrication appears to be the
dominant biogeochemical process in the lower strata controlling NO3-N concentrations. Furthermore, the
second Paleosol stratum limits the penetration of groundwater recharge to the lower strata, as its K value
is relatively low. This process suggests that groundwater in the strata below the second Paleosol layer may
contain a signicant amount of old water generated before 1930s when intensive farming started.
Nitrate-N concentrations in the old water produced during the time without intensive farming were very
low according to Madison and Burnett [1985]). Mixing of recent groundwater recharge (e.g., after 1930s) with

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relatively high NO3-N concentrations with the old water with much lower NO3-N concentrations would also
result in lower NO3-N concentrations in groundwater below 8.510 m.
The processes controlling NO3-N concentrations in groundwater at the lower strata merit further study, such
as examining the prole of groundwater age over depth, identifying sources of nitrate, monitoring redox or
O2 ux, and understanding concentration variations of other forms of nitrogen (including gaseous forms)
with depth. In addition, note that the bulge-like prole of NO3-N concentrations over well depth did not
occur in all well nests (Figure 5). The bulge-like pattern was most evident in the Field 3 wells, where manure
was applied earlier and NO3-N concentrations were highest. Nitrate-N concentrations tended to increase over
well depth in nests D and E of Field 1 and D of Field 2, consistent with Hallberg [1989] and Kolpin et al. [1994]
for claypan watersheds. However, these nests do not have wells deeper than 12 m, and thus, their trends may
not be complete. The nitrate-N concentrations tended to decrease in nests B and C of Field 1, which agrees
with Savard et al. [2007]. Like the claypan layer, it is possible that cracks exist in the second Paleosol stratum in
these locations. These cracks not only allow passage of groundwater recharge into the deeper layers with
elevated NO3-N concentrations but also change the redox condition and thus biogeochemical processes.
The inconsistency of NO3-N concentration trend with depth among locations reects heterogeneity of the
hydrogeological conditions and the history of fertilizer uses over the entire watershed.

6. Conclusions
This study examined the long-term NO3-N concentrations in groundwater in an agricultural claypan
watershed in north-central Missouri and analyzed the factors that control the spatial and temporal variations
of NO3-N concentrations in groundwater, particularly with well depth at scales ranging from individual well
nests to the whole watershed. Despite slow vertical hydraulic conductivity, claypan soils do not substantially
limit and restrict percolation of water and NO3-N. Instead, groundwater in this claypan watershed is overall
more susceptible to nitrogen-fertilizer applications than other nonclaypan agricultural watersheds. NitrateN in groundwater in this claypan watershed was transported from soil and surface water via preferential ow
paths conveyed by cracks and macropores in the claypan layer, and its concentrations were enhanced by
nitrication in the upper strata. The second Palesol stratum at 8.510 m below the land surface, with lowest
hydraulic conductivity and effective porosity, exerted vertical control on hydrologic transport and resulted in
accumulation of NO3-N at this depth. Denitrication apparently occurred in the strata below this relatively
impervious stratum due to an anaerobic environment. Groundwater in the lower strata also mixed with
recharge generated before 1930s when intensive farming had just started, with very low nitrate-N concentrations. As a result, NO3-N concentrations increased with depth above the relatively impervious stratum but
decreased with depth below it. However, this trend did not appear in all of the well nests, demonstrating
the spatial heterogeneity of hydrogeologic conditions at the eld and watershed scales combined with
varying history of land uses and fertilizer applications. This information improves our understanding of the
processes that control NO3-N transport to the groundwater system of a claypan watershed.
Acknowledgments
This study is supported by USDA-NIFAs
projects awarded to Lincoln University in
Missouri, including two Capacity Building
Grant projects (nos. 2011-38821-30956
and 2013-38821-21461), one Evans-Allens
grant (no. 0225140), and two 1890s Land
Grant University Water Center projects
(no. 2010-38821-21614). The water
quality data of rainfall, stream water,
and groundwater was obtained from
USDA-ARS Cropping Systems and
Water Quality Research Unit (CSWQRU)
through Sustaining the Earths
Watersheds, Agricultural Research Data
System (http://www.nrrig.mwa.ars.usda.
gov/stewards/stewards.html).

AL-QUDAH ET AL.

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