Estimating Background and Threshold Nitrate

Concentrations Using Probability Graphs

by S.V. Panno1, W.R. Kelly2, A.T. Martinsek3, and K.C. Hackley4

Abstract
Because of the ubiquitous nature of anthropogenic nitrate (NO2 3 ) in many parts of the world, determining
background concentrations of NO2 3 in shallow ground water from natural sources is probably impossible in most
environments. Present-day background must now include diffuse sources of NO2 3 such as disruption of soils and
oxidation of organic matter, and atmospheric inputs from products of combustion and evaporation of ammonia
from fertilizer and livestock waste. Anomalies can be defined as NO2 3 derived from nitrogen (N) inputs to the
environment from anthropogenic activities, including synthetic fertilizers, livestock waste, and septic effluent.
Cumulative probability graphs were used to identify threshold concentrations separating background and anoma-
lous NO3-N concentrations and to assist in the determination of sources of N contamination for 232 spring water
samples and 200 well water samples from karst aquifers. Thresholds were 0.4, 2.5, and 6.7 mg/L for spring water
samples, and 0.1, 2.1, and 17 mg/L for well water samples. The 0.4 and 0.1 mg/L values are assumed to represent
thresholds for present-day precipitation. Thresholds at 2.5 and 2.1 mg/L are interpreted to represent present-day
background concentrations of NO3-N. The population of spring water samples with concentrations between 2.5
and 6.7 mg/L represents an amalgam of all sources of NO2 3 in the ground water basins that feed each spring; con-
centrations >6.7 mg/L were typically samples collected soon after springtime application of synthetic fertilizer.
The 17 mg/L threshold (adjusted to 15 mg/L) for well water samples is interpreted as the level above which live-
stock wastes dominate the N sources.

Introduction a concentration above the threshold value, this indicates

The Concept of Background
The background concentration of a particular ele-
ment or species is used by geochemists in many applica-
tions. The basic premise for determining a background
concentration is to set a threshold value; if a sample has
1Corresponding author: Illinois State Geological Survey, 615
East Peabody Drive, Champaign, IL 61820; (217) 244-2456; fax
(217) 244-2785; panno@isgs.uiuc.edu
2Illinois State Water Survey, 2204 Griffith Drive, Champaign, IL
61820; (217) 333-3729; fax (217) 244-0777; kelly@sws.uiuc.edu
3Statistics Department, University of Illinois, 101 Illini Hall,
an ‘‘event.’’ Examples of events are the presence of an
economic ore deposit or an indication of contamination
in water (Sinclair 1974, 1991). However, determining
background values can be fraught with difficulties and
uncertainties, and errors in their determinations can lead
to poor economic and policy decisions (Runnells 1998).
Historically, background values were primarily of con-
cern to exploration geochemists and used in locating eco-
nomic ore deposits (Sinclair 1974). In recent decades, the
environmental field has borrowed the background concept
as a means of identifying and evaluating environmental
contamination. The USGS (2004) defines background

Champaign, IL 61820; (217) 333-2167; fax (217) 244-7190;
martinse@.uiuc.edu
4Illinois State Geological Survey, 615 East Peabody Drive,
Champaign, IL 61820; (217) 244-2396; fax (217) 244-2785;
hackely@isgs.uiuc.edu
Received July 2005, accepted April 2006.
Copyright ª 2006 The Author(s)
Journal compilation ª 2006 National Ground Water Association.
doi: 10.1111/j.1745-6584.2006.00240.x
concentration in its Water Basics glossary as ‘‘a concen-
tration of a substance in a particular environment that is
indicative of minimal influence by human (anthropo-
genic) sources.’’
Determining background concentrations for some
contaminants can be difficult, especially those that have
multiple and nonpoint sources, or are reactive in the envi-
ronment. Nitrate (NO2 3 ) is an example of an ion for which

Vol. 44, No. 5—GROUND WATER—September–October 2006 (pages 697–709) 697

determining a threshold concentration is complicated
because of its multiple natural and anthropogenic sources
and its reactivity (Panno et al. 2003). One of the problems
with setting a threshold nitrate-nitrogen (NO3-N) value is
that natural processes that affect NO3-N concentrations
can vary widely in time and space. It is commonly
observed that NO3-N concentrations decrease downgradi-
ent or with depth in aquifers (Larson and Henley 1966;
Smith et al. 1991; Altman and Parizek 1995; Tesoriero
et al. 2000; Böhlke et al. 2002; Puckett and Cowdery
2002; Tomer and Burkart 2003). This can occur within
a very small change in depth as the ground water crosses
a redox boundary (redoxcline), where oxygen and nitrate
abruptly disappear due to denitrification (Postma et al.
1991; Appelo and Postma 1994; Kelly 1997). These
boundaries can migrate with time, and in some aquifers,
especially those with low organic carbon and ferric iron,
there may be a limit as to how much NO2 3 can be reduced
(Smedley and Edmunds 2002). Thus, the depth of the
wells from which ground water samples are collected is
an important variable affecting the determination of back-
ground concentrations. Mixing of water of different ages
or from different source areas can also affect NO3-N con-
centrations and is an important process in karst areas.
Mixing can occur naturally (e.g., due to rapid recharge) or
due to well construction practices; in karst areas, wells
are often uncased over large depth intervals. Other impor-
tant variables include soil composition, lithology, thick-
ness of the unsaturated zone, and biological activity.
These variables can change within a ground water basin
or watershed as well as across multiple ground water
basins.
Nitrate contamination is primarily a concern in agri-
cultural regions and, to a lesser extent, urban areas. It has
been hundreds to thousands of years since there were no
human impacts on most of these environments; thus,
determining background concentrations for NO3-N with
respect to some ‘‘pristine’’ state may no longer be possi-
ble. Even prior to widespread application of synthetic fer-
tilizers, clearing and plowing of land occurred, both of
which can alter NO3-N concentrations by exposing
organic matter to the atmosphere and increasing oxidation
of organic N and leaching of NO2 3 to ground water
(Stevenson 1986; Calderón et al. 2001; Calderón and
Jackson 2002). Although these are clearly human activi-
ties, they are not typically accounted for when assessing
anthropogenic sources. Synthetic fertilizer and large-scale
livestock operations are the sources of anthropogenic N
contamination that are typically considered, with airborne
combustion products and discharge from private septic
systems and sewage-treatment plants accounted for in
some environments.
Because of the ubiquitous nature of NO2 3 in the envi-
ronment today and the large variety of human-related
sources, the term ‘‘background’’ cannot be defined as that
range of NO2 3 concentrations resulting from only natural
sources (atmospheric, wildlife, and degradation of natu-
rally derived soil organic matter in most environments).
This is especially true in agricultural regions, such as the
Midwestern United States. Background NO2 3 must now
be recognized to include soil organic matter from the
698 S.V. Panno et al. GROUND WATER 44, no. 5: 697–709
residue of fertilized and unfertilized crops, products of
combustion, and evaporation of ammonia (NH3) from
synthetic and organic N fertilizer and livestock waste, in
addition to naturally derived NO23 . We refer to this value
as ‘‘present-day background’’. The NO3-N in samples
with concentrations above present-day background levels
would be derived from the most obvious human-related
sources: synthetic N fertilizers, livestock waste, and
septic effluent.
Determining NO3-N Background Values
in Ground Water
Background values are typically determined either
temporally (what were concentrations prior to human
activity?) or spatially (what are concentrations in areas
unaffected by human activities?). The main method for
calculation of a temporal background is by evaluating
historical data. Spatial background values are usually
determined by collecting ground water samples from
pristine areas. Large data sets (hundreds or more sam-
ples) have also been evaluated, usually using descriptive
statistical measures, to determine background values; this
method is primarily spatial but can also include temporal
aspects. Each of these methods has advantages and dis-
advantages and has underlying assumptions that affect its
reliability and applicability.
Evaluation of large data sets is probably the most
useful technique for determining background and thresh-
old values on large scales. One of the most often-cited
studies of background values of NO3-N in ground water
in the United States is Madison and Brunett (1985). They
examined data from more than 87,000 wells throughout
the United States and determined that 0.2 mg/L was
the natural background level and that concentrations
>3.0 mg/L could probably be attributed to anthropogenic
effects. Their selection of this value was based, in part, on
the fact that for samples with concentrations >3.0 mg/L,
NO3-N was inversely related to well depth, while samples
with lower values had a depth distribution similar to that
of all the wells sampled. Others who have determined
background and threshold NO3-N concentrations from
large data sets include George and Hastings (1951), Parliman
(1988), Baker et al. (1989), Nolan (2001), Levine et al.
(2002), and Nolan and Hitt (2003). Their background
concentrations ranged from 0.08 to ~2 mg/L, and anthro-
pogenic events ranged from 2 to 4.5 mg/L (Table 1). In
evaluating large data sets, researchers generally must rely
upon the sampling and analytic techniques of others over
which they had no control. Data sets often do not repre-
sent a random or unbiased set of samples, and contami-
nated areas are often overrepresented (Helsel and Hirsch
1997). In addition to data integrity issues, there can be
difficulties in finding rigorous statistical techniques to
evaluate the data. The data are likely to not have a uni-
form distribution and have a large percentage of censored
values; these two limitations are both typical for NO3-N.
Using data from many locations can lead to ignoring
important differences, both natural and anthropogenic,
that can exist among ground water basins or watersheds.
The main assumption behind using historical data is
that they represent values prior to considerable human
 Table 1
Published Estimates of Background or Threshold Concentrations for NO3-N (mg/L). Some of the Publications
Also Determined Concentrations Indicating Anthropogenic Contamination

Anthropogenic Sources and Locations

Reference Background/Threshold Events (number of samples or sample dates)

Large Data Sets

George and Hastings (1951) 1–2 4.5 Wells, Texas (>20,000)
Madison and Brunett (1985) 0.2 3.0 Wells, United States (>87,000)
Parliman (1988) 1 2 Wells, Idaho (1678)
Baker et al. (1989) <0.3 Wells, Ohio (>14,000)
Nolan (2001) 4 Wells, United States (1230)
Levine et al. (2002) 0.08 Wells, Ohio (466)
Nolan and Hitt (2003) 1.1 Wells in undeveloped areas, United States (>12,000)
Historical Data Sets
Hallberg and Keeney (1993) <1 Wells and springs, Iowa (1930s)
Katz et al. (2002) 0.1 Springs, northern Florida (1950s)
Limbrick (2003) 1 Springs, UK (1880s–1940s)
Jones and Smart (2005)
2.1 Karst springs, UK (1930s)
Pristine Areas
McKenna et al. (1988) <1.3 Wells in natural areas, Illinois
Postma et al. (1991) <0.1 Pristine wells, Denmark
Mueller and Helsel (1996) <2 Wells, United States
Panno et al. (1996) 1.4 Springs and wells, Illinois
Leenhouts et al. (1998) 4.5 Background well, Arizona
Cho et al. (2000) <1.0 Upgradient well, South Korea
Brye et al. (2001) <0.3 Prairie soil water, Wisconsin
Perakis and Hedin (2002) 0.0019 Pristine streams, South America

influence or at least certain types of influence. Studies
that have evaluated NO3-N data collected prior to large-
scale application of synthetic fertilizers include Hallberg
and Keeney (1993), Katz et al. (2002), Limbrick (2003),
and Jones and Smart (2005) (Table 1). These data proba-
bly represent the best estimate of background values that
are available; however, the primary limitation in using
historic data is that such data sets are scarce.
Determining background NO3-N concentrations from
ground water samples collected in pristine areas is a com-
mon practice. In a highly cited publication, Mueller and
Helsel (1996) used data from ‘‘relatively pristine’’ sites
sampled as part of the USGS National Water-Quality
Assessment Program to define background NO3-N in U.S.
ground water as being <2 mg/L. Many other researchers
have collected samples from areas relatively uninfluenced
by human activities to estimate background NO3-N con-
centrations, with values varying from below detection
to >4 mg/L (McKenna et al. 1988; Postma et al. 1991;
Leenhouts et al. 1998; Cho et al. 2000; Brye et al. 2001;
Perakis and Hedin 2002; Nolan and Hitt 2003). It should
be noted, however, that there are areas in igneous and
metamorphic terrains of California that are capable of
generating NO3-N concentrations in surface streams as
large as 6.8 mg/L (Holloway et al. 1998). In addition, N
in sedimentary rock and sediments is associated with the
organic fraction (e.g., kerogen in shale) that may be
released to surface water and ground water during weath-
ering (Holloway and Dahlgren 2001).
Because of the long history of human impacts to the
global N budget, defining a pristine area can be
problematic. Pristine areas may have substantially different
physical, chemical, and biological characteristics than the
potentially impacted area(s). In an example from explora-
tion geochemistry, concentrations of metals in natural
water are orders of magnitude higher in mineralized areas
than in nonmineralized areas (Runnells 1998). With
respect to background NO3-N, if anomalies or events are
limited to NO2 3 derived directly from synthetic fertilizers,
livestock waste, and/or human sewage, background values
will include some anthropogenically derived materials.
These materials can include organic matter from crop resi-
due or tilled soils, products of combustion, and atmo-
spheric inputs due to evaporation of NH3 from fertilizer
and livestock waste, as well as natural sources.
In this paper, we use a statistical procedure borrowed
from exploration geochemistry to help define present-day
background concentrations for NO3-N and determine
threshold values separating sample populations having
different NO2 3 sources in karst aquifers of southwestern
Illinois. We believe this technique is an improvement over
calculated means/medians and other ways by which
background values for NO3-N have been determined and
applied. This procedure, in conjunction with other stat-
istical, analytic, and land-use data, provides information
about the background/threshold concentrations and the
nature of NO2 3 contamination in the study area.
Methods
All ground water samples were collected from
springs and wells fed by the karst aquifers of Illinois’
S.V. Panno et al. GROUND WATER 44, no. 5: 697–709 699
sinkhole plain, southwestern Illinois. Nitrate in ground
water in the study area should be associated with natural
soil processes and anthropogenic sources. The dominant
land use in the area is row-crop agriculture and small
livestock operations. Naturally occurring sources of NO2 3
from rock-water interactions should be minimal. The
karst-forming formations in southwestern Illinois are
Mississippian-age limestones of the Salem, St. Louis, and
Ste. Genevieve formations. The limestones are primarily
fine- to coarse-grained biocalcarenites with abundant fos-
sils (Willman et al. 1975) and contain very little organic
material. Shale interbeds are generally not found in the
karst region, and when they are, they are thin and organic
poor (Z. Lasemi, personal communication, 2005).
A total of 432 samples collected between 1994 and
2000 were compiled from several sources (Panno et al.
1996, 2001, 2003; Hackley et al. in press; Panno et al. in
press; supplementary material available as part of the
on-line article at http://www.blackwell-synergy.com); all
samples were collected by one or more of the authors of
this paper. Ground water samples were passed through
0.45-lm filters during collection, and the data represent
dissolved NO3-N. The data were divided into two groups
for statistical evaluation, one with 232 samples from
springs and seeps and the other with 200 well water
samples. The two groups represent distinct subsurface
environments that are expected to influence NO3-N
concentrations in different ways. Spring discharge repre-
sents an amalgam of soil water and shallow and deep
ground water draining into a central conduit system.
Water from point sources, such as septic effluent, mixes
with water from nonpoint sources, such as synthetic fertil-
izers, and water from forested areas. Conversely, the
ground water that is sampled in the wells, while intersect-
ing crevices and conduits, may undergo mixing of con-
taminated, near-surface sources with ground water from
deep (uncontaminated) sources.
The spring water samples were collected from 16
karst springs and 16 cave seeps and the well water samples
from 58 wells completed in the karst aquifer (Figure 1).
Well depths ranged from 6 to 190 m. One of the springs
and two of the wells were sampled 10 or more times; the
number of samples collected from the other springs,
seeps, and wells ranges from one to seven. In order to
assess the significance of the effects of (1) individual
springs or wells and (2) the date of sampling on NO3-N
levels, analysis of variance (ANOVA) was conducted on
two-way layout models with individual springs or wells
as one factor and date of sampling as the second factor.
Cumulative Probability Plots
Many data sets of the chemical composition of
ground water can contain one or more populations (e.g.,
background and anthropogenic contributions from one or
more sources). Consequently, the determination of a back-
ground concentration for a particular analyte can be diffi-
cult. The mean and standard deviation of a data set have
been used to estimate a background value using the mean
plus 2 standard deviations. This technique is arbitrary (in
the selection of the statistics) and does not consider
the possibility of the presence of multiple populations
700 S.V. Panno et al. GROUND WATER 44, no. 5: 697–709
(Sinclair 1974). In this study, we used cumulative proba-
bility plots, a technique borrowed from the field of
geochemical mineral exploration (Sinclair 1974, 1991).
Indicators, such as metal concentrations in rock, soil, or
water samples, can be divided into two or more pop-
ulations separated by inflection points on cumulative
probability graphs. The populations determined in this
manner are designated as background and one or more
‘‘anomalies,’’ and the concentrations at the inflection
points are defined as ‘‘threshold’’ values. In the context of
geochemical exploration, background is used as the base-
line concentration; anything above this threshold concen-
tration is interpreted as an anomaly and indicative of the
presence or influence of a mineral deposit (Sinclair
1983). We reasoned that the same technique could be
applied to water chemistry data where it should be possible
to separate natural sources from anthropogenic sources.
Important limitations to this approach are that a minimum
of ~100 values is needed and, as Sinclair (1991) states,
‘‘the determination of thresholds must be viewed as an
estimation procedure in the statistical sense, subject to
random and systematic error.’’
On cumulative probability plots, maximum curvature
of the lines reveals inflection points or threshold values
between populations. This is based on the fact that the
values of a single normally or lognormally distributed
population will form a straight line. Two or more mixed
populations will result in a curved line with a pronounced
inflection point(s). Those inflection points are thresholds
distinguishing two or more overlapping populations.
The NO3-N concentrations from spring (n ¼ 232)
and well samples (n ¼ 200) were log transformed prior to
plotting on separate cumulative probability plots. Class
intervals of 0.25 mg/L for springs and 0.20 mg/L for
wells were selected by trial and error in order to create
smooth curves on the probability plots, resulting in ~20
classes for each data set. The probability of each class
was calculated by consecutively adding the number of
samples in each set, in order, from highest concentration
to lowest. The cumulative number in each class was then
divided by n in order to calculate cumulative percent
probability. The midpoints between data classes were
plotted against cumulative percentages, and a relatively
smooth line was constructed connecting the data points.
Thresholds were chosen at the intersection of two ‘‘lin-
ear’’ segments of the probability curves. Because of the
paucity of data points at the extremes of the data set,
abrupt changes in slope may be present that reflect only
the incompleteness of the data set and not an inflection
point or threshold.
In addition to NO3-N concentrations, NO2 3 stable iso-
tope values were available for 28 well samples and atrazine
concentrations were available for 206 and 172 spring and
well samples, respectively (Panno et al. 1996, 2001, 2003;
Hackley et al. in press). Nitrate isotope data can be a useful
tool for identifying sources of NO2 3 in the environment, as
well as determining if denitrification has occurred (Heaton
1986; Aravena and Robertson 1998; Panno et al. 2001).
Chloride (Cl2) and bromide (Br2) data (Panno et al. in
press, supplementary material), land-use information, and
sample date were also used to help interpret NO2 3 sources
Figure 1. Map of southwestern Illinois’ sinkhole plain showing well and spring locations.
and the results from the NO3-N probability graphs. Plotting
Cl/Br vs. Cl2 and vs. total N (Panno et al. 2006) is a new
technique that can separate different sources of Cl2. All
the data used in this paper, sample locations, land use for
well water samples, and additional plots discussed herein
may be found in an Illinois State Geological Survey Open
File Series paper (Panno et al. in press) and in the journal’s
supplementary material.
Results
Basic Statistics and ANOVA Analysis
The median NO3-N concentrations in the spring and
well water samples were 4.6 and 1.0 mg/L, respectively.
Both data sets were nonnormally distributed and signifi-
cantly different as determined by the Mann-Whitney rank
sum test. The range of NO3-N concentrations was much
greater for the well water samples, between <0.01 and
80.9 mg/L compared to between 0.18 and 30.3 mg/L for
the spring water samples. Nitrate was detected in all the
spring water samples, while NO3-N was below detection
(0.01 mg/L) in 15% of the well water samples.
In the two-way ANOVA model with individual
springs and sampling dates as factors, the individual
spring was highly significant (P < 0.001), while the date
of sampling was not significant at all (P ¼ 0.912). In the
two-way ANOVA model with individual wells and dates
of sampling as factors, individual wells were significant
at the 0.1 level (P ¼ 0.077); date of sampling was again
not significant (P ¼ 0.160).
Cumulative Probability Graphs
Cumulative probability graphs of the NO3-N data for
the spring and well water samples are shown in Figures 2
and 3. Three thresholds (inflection points or changes in
slope) and four sample populations were identified for
both data sets. The threshold concentrations for the spring
water samples were ~0.4, 2.5, and 6.7 mg/L; the latter
two threshold values were similar to the 25th and 75th
S.V. Panno et al. GROUND WATER 44, no. 5: 697–709 701
percentile values of 2.98 and 5.78 mg/L, respectively. The
threshold concentrations for the well water data were
~0.1, 2.1, and 17 mg/L; only the lowest value was similar
to the 25th percentile (0.10), whereas the 50th and 75th
percentile values fell somewhere between the two
extreme threshold values (0.80 and 5.92 mg/L, respec-
tively). The lowest threshold concentration in both data
sets was interpreted as the upper bound for ground water
deriving most of its NO2 3 from precipitation. The next
highest threshold values from each data set were in-
terpreted as the upper bounds for present-day background
concentrations. Samples having NO3-N concentrations
>2.5 (springs) or >2.1 mg/L (wells) were thus defined as
representing land-based anthropogenic contamination
(beyond anthropogenic atmospheric and soil sources).
The apparent inflection point near the top of Figure 2 was
ignored because of the likelihood that it is an artifact of
plotting empty classes. The lower inflection point near
the bottom of Figure 3 was truncated because the very
small NO3-N concentrations of the samples were in-
terpreted to represent the effects of denitrification in
samples collected from wells in which conditions were
reducing (based on ground water chemistry [Panno et al.
in press, supplementary material]).
The eight sample populations (four for wells and
four for springs) determined by the probability graphs
Figure 2. Cumulative probability graph for 232 spring water samples (32 springs and seeps) showing threshold values.
A histogram and box and whisker plot of the data are also shown.
702 S.V. Panno et al. GROUND WATER 44, no. 5: 697–709
were tested for normality using the Kolmogorov-Smirnov
normality test. For the spring water samples, the two
populations with the lowest NO3-N concentrations had a
normal distribution. For the well water samples, the
population with the greatest NO3-N concentrations had
a normally distributed population. The other populations
had neither normal nor lognormal distributions.
Discussion
Statistical Considerations
The ANOVA results clearly indicate that there were
effects of individual springs, and perhaps effects of indi-
vidual wells, on NO3-N concentrations. This finding pro-
vides a cautionary note for the use of the methodology; it
is important that sampling be conducted, as in the present
investigation, at sites with a variety of land uses and
potential sources of NO2 3 . No particular site or small sub-
set of sites should provide the bulk of the data; rather, the
samples should be reasonably balanced with respect to
the land use and potential sources at sites and the region.
At the same time, the existence of individual site effects
provides an additional rationale for the cumulative proba-
bility graph methodology. Assuming balanced and repre-
sentative sampling, the site effects are reflected in the
Figure 3. Cumulative probability graph for 200 well water samples (58 wells) showing threshold values. A histogram and box
and whisker plot of the data are also shown.
thresholds established by the graphs and are thus properly
accounted for in determining background levels.
The successful application of the cumulative proba-
bility graph method does not require normally or lognor-
mally distributed data (Sinclair 1991). For springs, it was
clear from the histogram of the log NO3-N values
(Figure 2) that the overall distribution was not lognormal.
The inflection points on the probability graph indicated
an interpretable breakdown of the distribution of the log-
ged values, as follows: (1) above a logged value of 0.83
(original NO3-N value of 6.7 mg/L), the distribution was
skewed to the left with a relatively long right-hand tail,
similar to an exponential distribution; (2) between the
logged values of 0.4 and 0.83 (2.5 and 6.7 mg/L), the
distribution was skewed in the opposite direction, to the
right; and (3) between the logged values of 20.4 and 0.4
(0.4 and 2.5 mg/L), the distribution was fairly uniform.
For wells, there was an analogous breakdown (Figure 3).
Above a logged value of 1.2 (17 mg/L), the distribution
was again skewed to the left; between the logged values
of 0.3 and 1.2 (2.1 and 17 mg/L), the distribution was
fairly uniform; between the logged values of 21 and 0.3
(0.1 and 2.1 mg/L), the distribution was somewhat
skewed to the left. Fundamentally, the probability graph
approach split the overall distribution into distinct compo-
nents and, in so doing, identified threshold values.
Threshold NO3-N Concentrations
The spring water population with NO3-N concen-
trations <0.4 mg/L may represent near-pristine or the low
end of present-day background conditions in the conduit-
dominated ground water in the study area; the average
N concentration of precipitation in the area is ~0.6 mg/L
for 2003 (National Atmospheric Deposition Program
[NADP] 2004). There were only five samples in this pop-
ulation, thus defining them as a separate population may
not be warranted. All these samples were collected from
seeps in a cave draining small nonagricultural watersheds
during periods of high rainfall. It is likely that this was
runoff that passed rapidly through the soil zone via sink-
holes or associated macropores. The threshold at 2.5 mg/
L was interpreted to be the upper bound of present-day
background, and concentrations above this value were
considered to be events, samples for which there were
land-based anthropogenic sources. The background pop-
ulation (n ¼ 33) would likely include NO2 3 from some
anthropogenic sources, such as soil organic matter from
crop residues, combustion products (St. Louis is <50 km
away and generally upwind of the study area), and evapo-
ration of NH3 derived from synthetic fertilizer. For the
population with NO3-N concentrations between 2.5 and
6.7 mg/L, the anthropogenic sources of NO2 3 contamina-
tion were an amalgam of N fertilizer, animal waste, and
S.V. Panno et al. GROUND WATER 44, no. 5: 697–709 703
septic effluent. This was by far the largest population of
spring water samples (n ¼ 165), highlighting the vulnera-
bility of karst systems to surficial contamination. The
land use in the ground water basins from which samples
with NO3-N concentrations >6.7 mg/L came was domi-
nated by row-crop agriculture. More than half of these
samples were collected in late May or June and thus may
have contained NO2 3 from N fertilizer applied in the
springtime (typically late April or early May) that had
been flushed out by heavy rains.
There were many more samples in the population
with the lowest NO3-N concentration for the well water
samples compared to the spring water samples (n ¼ 38),
even though the threshold concentration was slightly
lower (0.1 vs. 0.4 mg/L). This population is primarily
made up of wells located in areas where land use was
primarily nonagricultural (Figure 4) or very deep wells
where conditions can be anoxic (Panno et al. in press,
supplementary material). Well water samples are more
likely to have lower NO3-N concentrations than spring
water because they are relatively more protected from
surficial contamination (longer flow paths), and denitrifi-
cation is likely to be more substantial due to longer resi-
dence times and a potentially greater component of soil
water and matrix flow. Further, most of the ground water
samples collected showed evidence of denitrification
(Figure 5; Panno et al. in press, supplementary material);
it is likely that some of the samples with NO3-N concen-
trations <0.1 mg/L were affected by denitrification within
the soil zone and/or localized areas within the karst aqui-
fer. Defining 0.1 mg/L as the natural background in well
water samples, however, is not warranted because of the
proximity of agricultural contamination to even poten-
tially pristine wooded areas within the study area. For
example, total N in precipitation from pristine forests of
the Pacific Northwest of the United States is as low as
0.02 mg/L (NADP 2004). Given that NO3-N concen-
trations in spring water in the study area during and fol-
lowing rainfall events reflect the NO3-N concentration
in precipitation, it follows that natural background for
NO3-N within the karst aquifer was probably <0.1 mg/L.
There is evidence that shallow and deep ground
water mix in some wells because many wells are uncased
below the soil-bedrock interface in the study area (Panno
et al. 1996). Thus, NO3-N concentrations can be elevated
(up to 30 mg/L) in even the deepest wells of the study
area. The threshold value at 2.1 mg/L was interpreted as
being the upper limit of present-day background, compa-
rable to the 2.5 mg/L value found for the spring water
data. The slightly lower concentration for the well water
samples suggests that the well water samples had under-
gone more denitrification than the spring water samples.
The far greater percentage of spring water samples above
present-day background also indicates that the well water
samples were less likely to be impacted and more likely
to have undergone denitrification. The NO2 3 in samples
with NO3-N concentrations between 2.1 and 17 mg/L was
primarily from N fertilizer and septic effluent; these sam-
ples were collected from areas dominated by row-crop
agriculture and in the vicinity of a private septic system.
Well water samples with concentrations exceeding 17 mg/L
704 S.V. Panno et al. GROUND WATER 44, no. 5: 697–709
Figure 4. Box and whisker plot of NO3-N concentrations in
well samples based on predominant land use in the area. The
Livestock category generally includes wells in areas with
both row crop and livestock land use.
were probably dominated by animal waste; these samples
were collected from relatively shallow wells that were in
very close proximity to livestock (Panno et al. in press,
supplementary material).
Even though spring water samples were more likely
to exhibit NO2 3 contamination than well water samples,
their concentration range was much smaller (Panno et al.
in press, supplementary material). This is probably due to
the greater mixing of water from different areas within
conduits; consequently, point sources of contamination
can go unrecognized in spring water samples. Conversely,
a contaminated well would be diluted or flushed out at
a somewhat slower rate than a contaminated spring. Well
water compositions can reflect the effects of both point
and nonpoint sources. An additional factor is that soil and
sediment stored in conduits may be a fairly continuous
source of NO2 3 to the springs, through dissolution and
oxidation of organic matter (Panno and Kelly 2004).
Thus, there would be elevated NO3-N concentrations in
springs even during periods when one would expect low
concentrations, such as the late summer.
The present-day threshold NO3-N values of between
2.1 and 2.5 mg/L in this karst environment are similar to
the most commonly cited values for ground water in the
United States; for example, the threshold value used by
the USGS for shallow ground water is 2.0 mg/L (USGS
2002). However, our technique identified two additional
thresholds, one for present-day precipitation at ~0.4 mg/L
(similar to the threshold value for surface streams of 0.6
mg/L [USGS 2002]), and one for ground water containing
animal waste at ~17 mg/L.
Other Chemical Data
The NO2 3 isotope and pesticide data and land-use
information and Cl/Br plots (this investigation; Panno et al.
in press, supplementary material) support the threshold
Figure 5. d15 NO23 vs. NO3-N for 28 well water samples (data from Hackley et al. in press). Wells contaminated with animal
waste have high NO3-N concentrations (>15 mg/L). Arrow indicates increasing d15NO2
decrease due to denitrification.
values and interpretations of sources determined from the
probability graphs. A plot of d15N values vs. NO3-N con-
centrations for 28 of the well water samples (data from
Hackley et al. in press) shows a sample population with
elevated NO3-N concentrations (>15 mg/L) and d15N val-
ues between 8& and 13& (Figure 5). All these samples
were collected at farms from wells located in close prox-
imity to livestock and were determined, by Hackley et al.
(in press), to have been affected by animal waste. Nitrate
from soil or synthetic fertilizer sources tends to have rela-
tively low d15N values, <10& and typically <5& in Illi-
nois, while NO2 3 from livestock waste or septic systems
has somewhat larger d15N values, generally between 8&
and 20& (Hackley et al. in press). The picture is compli-
cated by denitrification; as NO2 3 is degraded, the d N
15
value of the NO2 3 remaining in solution increases. We
conclude from these and land-use data that the NO3-N
from the samples with concentrations >15 mg/L were pri-
marily from livestock waste, while the NO3-N in samples
with lower concentrations and similar or lower d15N val-
ues were primarily from the degradation of soil organic
matter and synthetic fertilizer sources. The data points
clustered along and to the left of the denitrification vector
in Figure 5 were all from wells located in cropped areas.
The 15 mg/L concentration separating livestock waste from
soil/synthetic fertilizer sources is commensurate with the
threshold values determined from the well water probabil-
ity graphs (17 mg/L). It appears that for wells with NO3-
N concentrations <15 mg/L, the shallowest wells (<50 m),
presumably with the youngest water, have undergone less
denitrification than most of the deeper wells.
Most of the samples with concentrations between the
present-day threshold value of 2.1 and 15 mg/L had d15N
values between 2& and 10& (Figure 5). Land use in the
vicinity of these well water samples was predominately
row-crop agriculture. Consequently, the NO2 3 was most
3 values as NO3-N concentrations
likely from synthetic fertilizer and soil organic carbon;
the decreasing NO3-N concentrations with increasing
d15N values is suggestive of denitrification (Hackley et al.
in press). The two samples with NO3-N concentrations
<2.1 mg/L and d15N values >20& had probably under-
gone considerable denitrification, although the original
source for these samples was no longer determinable. The
other samples with NO3-N concentrations <2.1 mg/L may
represent present-day background conditions or minor
amounts of denitrification.
About 19% of the well samples had detectable atra-
zine. Those with detectable atrazine had significantly
greater NO3-N concentrations than samples without
(median ¼ 6.4 mg/L vs. 0.21 mg/L), and more than 90%
of the samples with detectable atrazine had NO3-N con-
centrations greater than the estimated present-day back-
ground of 2.1 mg/L (Figure 6). Atrazine is obviously an
anthropogenic contaminant, and its absence from samples
with NO3-N concentrations <2.1 mg/L is additional evi-
dence that 2.1 mg/L is an appropriate present-day thresh-
old concentration in this area. In contrast, ~70% of spring
samples had detectable atrazine, and the difference in
NO3-N concentrations between samples with and without
atrazine was not significant (Figure 6). This is additional
evidence that there is considerable mixing of water from
different areas within conduits that discharge at springs.
The separation of well water samples affected by ani-
mal waste, septic effluent, and row-crop agriculture was
also accomplished through the use of a recently developed
technique using Cl/Br vs. Cl2 and other related plots
(Panno et al. 2006, in press, supplementary material).
Natural Background vs. Present-Day Background
Most published NO3-N concentrations identified as
indicating anthropogenic contamination range from 0.08 to
4.5 mg/L (Table 1). Several factors contribute to this wide
S.V. Panno et al. GROUND WATER 44, no. 5: 697–709 705

Figure 6. NO3-N concentrations as a function of atrazine
detection in 172 well water samples and 206 spring water
samples. Threshold values of 2.1 and 15 mg/L determined
from cumulative probability graph for well water samples
are shown. Of the well water samples with nondetectable
atrazine, 28 had NO3-N concentrations below the detection
limit (0.01 mg/L).
Figure 7. Nitrogen sources for the different sample populations. Sources for a particular population include those for
populations with lower NO3-N concentrations. NO3-N concentrations determined for spring and well water samples from
Figures 2 and 3.
706 S.V. Panno et al. GROUND WATER 44, no. 5: 697–709
range, including that estimates were made using different
techniques and for diverse environments. An important con-
sideration is that investigators have defined two separate
background values, one for natural and one for present-day
conditions. Natural background NO3-N concentrations in
shallow ground water should by definition include only
NO2 3 from dissolved geological N or in recharge water in
areas unaffected by humans. This would be limited to natu-
ral atmospheric inputs, natural organic matter degradation
in soils and the saturated zone, wildlife waste, and dissolu-
tion of N-containing minerals (Figure 7). Ideally, natural re-
fers to presettlement conditions, but because there are
essentially no presettlement data, natural background values
are generally determined for samples collected in natural
areas, such as forests and prairies. Unfortunately, in much
of the world, especially in intensively farmed areas such as
the Midwestern United States, there are very few natural
areas and the ones that do exist are not particularly pristine.
For example, humans are responsible for nearly doubling
the amount of fixed N entering land surface on a global
scale (Tilman et al. 2001). Combustion products from coal
burning and vehicle exhaust and NH3 volatilized from syn-
thetic fertilizers contribute to atmospheric inputs over large
regions. In addition, most forests and prairies have not con-
tinuously existed since presettlement times but represent
new growth.
 Defining a pristine natural background value for
NO3-N may be impossible and pointless in many environ-
ments. If the goal of defining background is to determine
when an anthropogenic event has caused contamination,
then defining a present-day background value may be a
more meaningful and useful goal. Nitrate contamination
ofinterest is usually due to excess leaching of fertilizer or
discharge of livestock or human waste water but could
also include land-use practices such as till vs. no till
(Figure 7).
Present-day background values will include some
anthropogenic sources for most environments, primarily
atmospheric inputs and soil tillage (Figure 7). The total
concentration of N in present-day rainfall in our study
area (NO2 1
3 , NH4 , organic N) is ~0.6 mg/L, which is con-
siderably higher than more isolated and more pristine
areas such as the forests of the Pacific Northwest, where
concentrations range from 0.02 to 0.17 mg/L (NADP
2004). The role of soil tillage and degradation of crop
residue on NO3-N concentrations in ground water is
poorly understood, but farm management studies suggest
that farm practices can have a substantial effect (Calderón
and Jackson 2002; Randall et al. 2003; Tomer and
Burkart 2003). The combination of these anthropogenic
factors appears to increase background NO3-N con-
centrations (from natural to present day) by at least 1 mg/
L in our study area as well as other areas reported in
Table 1.
Conclusions
Attempting to determine natural background values
for NO3-N is generally not useful because of the wide-
spread nature of NO2 3 contamination in the environment,
especially airborne N and soil tillage. Natural background
NO3-N concentrations in ground water in the United
States were probably <1 mg/L in most environments,
but present-day background values are higher. In the
sinkhole plain of southwestern Illinois, present-day back-
ground in ground water was estimated to be 2.1 to
2.5 mg/L.
Synthetic fertilizer and human and livestock waste
are the primary sources of NO2 3 in ground water environ-
ments with concentrations above present-day background.
In the sinkhole plain area, leaching of synthetic fertilizer
can elevate NO3-N concentrations above background lev-
els to concentrations as high as 15 mg/L. Recharge con-
taining animal waste can increase NO3-N concentrations
in ground water even higher, with several samples having
concentrations >30 mg/L and one >80 mg/L.
This investigation shows that the cumulative proba-
bility technique is a viable means of separating back-
ground from anomalous concentrations of NO3-N in karst
ground water. This technique could be used in other areas
to help identify background concentrations for NO3-N, as
well as other ions in ground water. Applying such a
technique gives more meaningful values than relying
on single threshold values determined in other inves-
tigations for different parts of the world, which may have
substantially different processes affecting contaminant
concentrations.
Supplementary Material
The following supplementary material is available
for this article:
Database for Estimating Background and
Threshold Nitrate Concentrations Using Probabil-
ity Graphs.
Figure 1.
Figure 2.
Figure 3.
Figure 4.
Figure 5.
Figure 6.
Figure 7.
Figure 8.
Figure 9.
Figure 10.
Figure 11.
Figure 12.
Figure 13.
Figure 14.
Table 1.
Table 2.
This material is available as part of the online
article from: http://www.blackwell-synergy.com/doi/
abs/10.1111/j.1745-6584.2006.00240.x (This link will
take you to the article abstract).
Please note: Blackwell Publishing are not respon-
sible for the content or functionality of any supple-
mentary materials supplied by the authors. Any
queries (other than missing material) should be
directed to the corresponding author for the article.
Acknowledgments
The authors thank Don Keefer (Illinois State Geolog-
ical Survey) and Tom Holm (Illinois State Water Survey)
for their critical reviews of the manuscript and Pam
Carrillo for preparation of the figures. We also thank
Brian Katz, Ed Harvey, and an anonymous reviewer for
providing excellent suggestions for improving the manu-
script. This research was supported with funds from the
Illinois Department of Natural Resources, Illinois State
Geological and Water Survey divisions. Publication
of this article has been authorized by the Chiefs of the
Illinois State Geological and Water Surveys.
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