WATER RESOURCES RESEARCH, VOL. 42, W08434, doi:10.

1029/2005WR004419, 2006
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Investigating the applicability of end-member mixing analysis
(EMMA) across scale: A study of eight small, nested catchments in
a temperate forested watershed
April L. James1,2 and Nigel T. Roulet1,3
Received 12 July 2005; revised 14 March 2006; accepted 2 June 2006; published 30 August 2006.
[1] Current interest in multicatchment hydrologic studies challenges the use of
geochemical mixing models across scale, where changes in stream water chemistry
from catchment to catchment may indicate (1) changes in the proportional
contributions of end-members, (2) changes in the geochemical signatures of end-members in
space, or (3) changes in the geochemical signatures of end-members in time. In this study we
examine stream water chemistry from a series of eight nested catchments in a 1.47 km2
temperate forest watershed in southern Quebec for evidence of contributing end-members.
We use eigenvector and residual analysis (Hooper, 2003) of the multivariate stream water
chemistry records to estimate the dimensionality of the mixing space for each individual
catchment, indicating the number of contributing end-members. Using the mixing
space of the largest, highest-order catchment (1.47 km2), we evaluate its ability to predict
stream water chemistry in the seven upstream catchments, representing progressively
smaller areas. We observe significant spatial variation in ionic mixing ratios within the 147 ha
watershed. Only spatial testing across catchments allowed us to identify appropriate
conservative tracers most compatible with the application of a single mixing model across
scale. On the seasonal timescale, groundwater geochemistry changes significantly due to the
recharge from spring snowmelt, indicating a mixture of two groundwater end-members of
varying age. On the timescale of storm events, shallow perched water and throughfall
provide geochemical signatures consistent with physical mixing while unsaturated zone soil
water sampled from local pockets of glacial till does not. Our results suggest cautious
application of end-member mixing analysis (EMMA) for multicatchment studies.
Citation: James, A. L., and N. T. Roulet (2006), Investigating the applicability of end-member mixing analysis (EMMA) across
scale: A study of eight small, nested catchments in a temperate forested watershed, Water Resour. Res., 42, W08434,
doi:10.1029/2005WR004419.

1. Introduction separation and end-member mixing analysis (EMMA)

[2] Detailed empirical studies of runoff generation are
moving beyond the simplifying confines of headwater
catchments to include larger spatial extent [e.g., Mulholland
et al., 1990; Fan, 1996; Brown et al., 1999; Shanley et al.,
2002; McGlynn et al., 2004]. In doing so, these studies
address how catchment hydrological and biogeochemical
properties and processes vary across scale. One approach to
the analysis of hydrologic response across multiple catch-
ments has been to compare the varying contributions of
source waters to the stream channel by using mixing models
that rely on natural tracer techniques. Mixing-models iden-
tify different temporal and/or geographical sources of water
that contribute to stream flow and are used for hydrograph
1
Department of Geography, Global Environment and Climate Change
Centre, McGill University, Montreal, Quebec, Canada.
2
Now at Department of Forest Engineering, Oregon State University,
Corvallis, Oregon, USA.
3
McGill School of Environment, McGill University, Montreal, Quebec,
Canada.
Copyright 2006 by the American Geophysical Union.
0043-1397/06/2005WR004419$09.00
W08434
[Genereux and Hooper, 1998; Hooper, 2001, 2003].
[3] Natural tracer techniques take advantage of the chem-
icals and chemical isotopes in the catchment environment to
investigate flow paths, water residence times, and transport
and transformations of chemical solutes and nutrients [e.g.,
Sklash et al., 1986; Stewart and McDonnell, 1991; Bazemore
et al., 1994; Gibson et al., 2000]. The use of natural tracer
techniques has arisen, in part, because of the difficulty of
measuring storm flow generation at the hillslope and catch-
ment scales [Bazemore et al., 1994]. They provide an
integrated response at the scale of individual catchments with
an immediate link to hydrologic flow paths [Sklash, 1990;
Kendall, 1993; Genereux and Hooper, 1998].
[4] EMMA relies on the assumptions of linearity of the
mixing process, the conservative behavior of tracers, and
the time invariance of end-member compositions [Hooper,
2001, 2003]. End-members represent the chemical compo-
sitions of source waters existing within a catchment that
undergo physical mixing only during travel time to the
stream channel. In the development of two- and three-
component mixing models, geochemical and/or isotopic
signatures of end-members have been estimated directly
from field sampling [e.g., Mulholland et al., 1990; Hangen
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W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE
et al., 2001; Scanlon et al., 2001]. Hooper [2003] offers an
alternative inverse approach where eigenvector and residual
analysis of observed stream water chemistry estimates the
number contributing end-members. End-members charac-
terized by direct sampling in the field are then screened for
their ability to fit into the mixing space created by the
analysis of observed stream water chemistry.
[5] Recent studies have used data sets of varying spatial
and temporal extent in their evaluation of contributing
source waters and flow paths [Hooper et al., 1990; Brown
et al., 1999; Kendall et al., 1999; Katsuyama et al., 2001].
For a single summer storm event, Brown et al. [1999] use
EMMA to examine runoff generation across a series of
seven nested headwater catchments (8 to 161 ha) at Shelter
Creek, Catskill Mountains, New York. Three end-members,
throughfall, O-horizon water, and groundwater were identi-
fied as contributing to summer storm runoff. For this large
storm event on dry antecedent moisture conditions, shallow
subsurface flow can develop and deliver O-horizon water,
identifiable by high dissolved organic carbon (DOC) con-
centrations to the stream channel. During the March – May
1996 spring snowmelt at Sleepers River, Vermont, Kendall
et al. [1999] identified two contributing sources and flow
paths for the 41 ha headwater catchment: (1) a shallow flow
path, attributed to an O-horizon or overland flow, charac-
terized by low base cation and silica concentrations and
high DOC, and (2) a groundwater from a deep flow path,
exhibiting high base cation and silica concentration and low
DOC. Both hillslope till and soil water were rejected as
potential end-members.
[6] The extensive analysis performed at the Panola Mountain
Research Watershed (PMRW), Georgia, has made use of a
multiyear stream chemistry record to identify contributing
end-members [Christophersen et al., 1990; Hooper et al.,
1990; Christophersen and Hooper, 1992; Hooper, 2001,
2003]. Analysis at the 41 ha catchment scale [Hooper et
al., 1990] proposed three contributing end-members to
stream flow: a shallow organic A-horizon soil water, flood-
plain groundwater, and a hillslope or upper catchment
groundwater (termed ‘‘upper GW’’ by Hooper [2001]).
However, Christophersen and Hooper [1992] found the
A-horizon end-member did not fit into the stream water
chemistry mixing space created by eigenvector analysis. A
more recent study of PMRW at the 10 ha scale [Burns et al.,
2001] found strong storm-based contributions from riparian
groundwater and outcrop runoff with small but significant
contribution from hillslope runoff. The influence of outcrop
runoff at this 10 ha scale, where granite outcrop covers over
30% of the total area, is considerable.
[7] Certainly, the assumptions involved in the application
of mixing models in catchment hydrology are challenged
by the complex spatial and temporal heterogeneity of
the catchment environment. Breakdown of the multiyear
41 ha PMRW data set indicated a temporal change in the
geochemical signature of the A-horizon end-members
[Hooper, 2001, 2003] with sulfate and calcium concentra-
tions decreasing by 50% from 1988 to 1991. Changes in
stream water concentrations during this time appear consis-
tent with the temporal change in the A-horizon end-member.
Seasonal changes in groundwater geochemistry will also
challenge the assumption of time-invariant end-members
[Rademacher et al., 2005].
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W08434
Figure 1. Westcreek watershed, Mont Saint-Hilaire,
Quebec, Canada. Eight small catchments are defined within
the watershed by location of gauging stations and surface
topographic analyses. Independent sampling of source water
end-members were collected from instruments installed
along two transects (T1, T2) and from a perennial spring
located immediately above the Sc gauging station.
[8] Strong evidence exists for spatial variation in soil
water and groundwater signatures [e.g., Katsuyama et al.,
2001]. Even within the 490 m2 artificial grassland catch-
ment Hydrohill located near Nanjing China, Kendall et al.
[2001] observed large variability in groundwater concen-
trations of SiO2 and chloride. Spatial variation in bedrock
geology, and soils can alter geochemical signatures of
terrestrial water by mineral dissolution and potentially
necessitate more spatially complex mixing models. Inter-
estingly, in an analysis of six different catchments at
PMRW, Hooper [2003] suggests that surface exchange
reactions promoted by immobile water in ephemeral catch-
ments, not mineral dissolution, may be the cause of the
variation in ion mixing ratios observed from different
catchments.
[9] In this study, we apply the diagnostic tools of
Hooper [2003] to evaluate contributing source waters
across areas of 7 to 147 ha within a series of small nested
catchments of temperate forest in southern Quebec,
Canada (Figure 1). We are interested in determining
(1) the dimensionality (or number of end-members) re-
quired to explain the observed outflow stream chemistry,
and an evaluation of this dimensionality across scale,
(2) what solutes can be assumed to be conservative in
their behavior for implementation of EMMA across scale,
and (3) a hydrological interpretation of contributing geo-
graphical source waters across scale specific to our field
site. We hypothesize that the dimensionality of each
catchment is the same, indicating the presence and mixing
of the same number of end-members independent of scale
but that the contributions of end-members may certainly
change with scale. There exist only a few studies that
apply EMMA across scale and fewer still that have tested
the working assumption of conservative solute behavior
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE W08434

Figure 2. Bedrock geology of Mont Saint-Hilaire (MSH). The Westcreek watershed of this study
overlies the southwestern quadrant of the geologic map of MSH where bedrock is dominated by the
Sunrise and Pain de Sucre suites. A black circle indicates the outlet of the Lk catchment (Figure 1) into an
internal lake, Lake Hertel, from the western side of the mountain. Figure provided by the B. Hamel, MSH
Nature Reserve, digitized from Currie [1983]. Reproduced in digitized format with kind permission of
the Minister of Public Works and Government Services Canada, 2006, and Courtesy of Natural
Resources Canada, Geological Survey of Canada.

across scale [e.g., Hooper, 2003]. Testing of these hypotheses
and model assumptions across multiple catchments is a major
contribution of this study. Physical interpretation of the
contributing end-members is performed by screening ‘‘po-
tential’’ end-members independently sampled in the field
against the eigenvector analysis of stream water chemistry.
2. Study Site
2.1. Physical Characterization
[10] Mont-Saint-Hilaire (MSH) is a forested UNESCO
biosphere reserve and one of 10 Monteregian hills located
in southern Quebec, Canada. Climate in this region is
humid-continental, with daily mean temperature norms for
January and July of
10.3
C and 20.8
C, respectively.
The region receives an average annual precipitation of 940
mm, 22% of which comes in the form of snow (Meteo-
rological Survey of Canada). Precipitation is relatively
uniform throughout the year, although a strong seasonality
in base flow exists due to spring release of snowmelt and
increased evapotranspirative demands during the growing
season. MSH is one of 13 remaining areas of old-growth
deciduous forest in the St. Lawrence River valley. Sugar
maple and American beech are the dominant species of
trees with some sugar maples aged over 400 years old.
[11] The mountain is plutonic in origin, rising 350 m
above the surrounding lowlands of the St. Lawrence. In the
1970s, K. L. Currie mapped the entire mountain, producing
a detailed map of bedrock composition [Currie, 1983].
Recently digitized by B. Hamel (Gault Nature Reserve,
Quebec, 2005), this map (Figure 2) illustrates the complex-
ity of the bedrock geologic composition underlying the
Westcreek watershed located in the southwestern quandrant.
The three plutonic intrusions that formed MSH during the
Cretaceous period have resulted in bedrock made up of
essexite, predominantly gabbros, on the western side of the
mountain where the Westcreek watershed is situated. Chem-
ical compositions of the various suites of rocks [Currie,
1983] suggest that geographic source waters (end-members),
and in particular groundwater, could potentially experience
different ionic mixing ratios (e.g., Mg2+, Ca2+) as water
moves internally within the watershed, resulting in spatially
variable geochemical signatures and violating the assumption
of spatially uniform end-member signatures.

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W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE W08434

[12] For the purpose of this study, the Westcreek water- Table 1. Small Catchments Defined Within the Westcreek
shed is divided into variably nested small catchments defined Watershed and Their Nested and Hydrologic Statusa
by the location of stream gauging stations and topographic
analysis of a high-resolution digital surface elevation model. Hydrologic Number
Catchment Area, ha Nesting Status of Samples
These internal catchments range in size from 7 to 147 ha
(Figure 1). The Lk catchment is the largest catchment Lk 147 total outflow perennial 123
(147 ha) and the most downstream gauging station located Ef 91 Lk perennial 100
Pw 54 Lk perennial 124
at the outflow of the Westcreek watershed into a local lake Sc 38 Pw, Lk perennial 125
(Lake Hertel). Table 1 lists the series of catchments defined Sb 7 Sc, Pw, Lk ephemeral 50
within the Westcreek watershed and their nested and hydro- Yv 30 Sc, Pw, Lk ephemeral 95
logic status (ephemeral versus perennial). Vc 11 Ef, Lk ephemeral 96
[13] Soils at MSH originate from weathering of the Aw 11 Yv, Sc, Pw, Lk perennial 129
Seep ... Sc, Pw, Lk perennial 124
parent igneous intrusions beginning after the Pleistocene
a
glaciation [Webber, 1965]. In addition, lower elevations Nesting lists the downstream gauging stations for each catchment.
within the mountain (up to 170 m) were influenced by the
postglacial Champlain sea [Webber, 1965]. On the hill-
slopes, soils are well drained and can range in depth from
10 cm to 1.5 m (e.g., Figure 1, T1 transect in Aw traveled through the canopy, was sampled immediately after
catchment). In the valley bottoms, soils can be >2 m and each storm event from a series of 18 bucket collectors located
perched water tables can form due to the presence of a low- beneath the deciduous canopy throughout the 147 ha water-
permeability layer, or fragipan [Dingman, 1994], within shed. The resulting geochemical data set includes sampling
30– 50 cm of the surface. This layer is limited in extent and of base flow and storm runoff under varying antecedent
does not appear on the hillslopes. Along the T2 transect (Vc moisture conditions similar to those of Scanlon et al.
catchment), soil thickness can be very shallow (30 cm) on [2001], from wet conditions observed in early spring after
the gently sloping hillslope but maximum depths in the snowmelt to much drier conditions of early fall. This record
valley bottom are unknown. Variation in soils and the provides opportunity to observe changes in stream water
presence of pockets of glacial till are also a potential source chemistry over the course of both seasonal and storm-based
of spatially changing geochemical signatures. changes in contributing geographical source waters.
[16] The geochemical signatures of source waters (end-
2.2. Current Hydrologic Understanding members) potentially contributing to the stream channel
[14] At MSH, catchment storage is typically very high in were sampled from a series of groundwater and perched
the spring due to the release of large amounts of water water wells, piezometers, and soil water lysimeters located
during spring snowmelt. During these wet conditions, the along two transects, T1 and T2, in the Aw and Vc catch-
valley bottoms show extensive areas of saturation, a func- ments, respectively (Figure 1). Groundwater and perched
tion of high water tables, and the presence of localized water wells were dug and/or augered by hand, installed with
shallow fragipan on which perched water forms. As the PVC pipe screened the entire soil depth, and carefully
summer season progresses, storage is depleted due to stream backfilled. Perched water wells were installed in valley
flow and evapotranspirative demand. Under these drier bottom areas to depths above the local fragipan. For
conditions, the saturated areas within the valley bottoms groundwater wells where bedrock was deeper than could
disappear. However, during individual storm events, tran- be reached by digging or hand augering, stainless steel
sient saturation will occur in the valley bottoms on the piezometers were driven through the bottom of the well
shallow fragipan (potentially a function of both lateral flow prior to backfilling to reach a maximum depth. Piezometers
from the hillslopes and impeded infiltration at the depth of included a plastic tube insert running from the 0.5 foot
the fragipan), connecting and delivering water to the stream (15 cm) screen to ground surface to avoid contamination of
channel. We hypothesize that this perched water, in addition water samples drawn from depth. Along the steep hillslope-
to riparian groundwater and throughfall, is an important valley bottom transect T1, five groundwater wells range in
end-member and could distinguish itself with a unique depth from 0.8 to 2.3 m and three piezometers from 1.9 to
geochemical signature, particularly under these drier con- 2.6 m. The three piezometers are estimated to be screened
ditions. Previous studies have identified a shallow subsur- just above the mineral soil-bedrock interface. Along the
face flow path active during events [Kendall et al., 1999; more gently sloping transect T2, wells extended to depths of
Brown et al., 1999]. This perched water is potentially a 1.0 m and piezometers to depths of 1.5 m. All groundwater
component of water delivered via the shallow subsurface riparian wells and piezometers were sampled on a bimonthly
flow path that has been identified as an important end- schedule. Although groundwater wells were installed on the
member to stream water chemistry. hillslope along both transects, no hillslope groundwater was
successfully sampled from these wells.
[17] Along transect T1 (Aw catchment), soil water lysim-
3. Methods eters were installed to sample water from a depth of 35–
3.1. Field Sampling and Laboratory Methods 40 cm with three lysimeters located on the hillslope and
[15] Stream water was sampled at each catchment gaug- three in the valley bottom. On the hillslope, lysimeter depths
ing station, prior to, during, and after 12 storm events using extended into the mineral soil. In the valley bottom,
instantaneous grab samples during spring to fall field lysimeters were located above the shallow fragipan at
seasons of 2001 and 2002. Throughfall, rainfall that has 40 cm. Along transect T2 (Vc catchment), hillslopes are
of lower relief with shallow soils extending into a variably
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W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE
Table 2. Analytical Precision for Solutes as Expressed as a
Percent of Average Concentrations From Lk (147 ha) Stream
Watera
Solute Analytical Error, % Residuals, %
Na+ 8.3 7.6
Mg2+ 29.1 6.9
Ca2+ 7.8 5.1
EC 1.1 10.3
ALKb 15.2 5.9
a
Corresponding residuals (average magnitude) are shown for 1-D Lk
(147 ha) mixing space (see also Figure 6). Residuals are also expressed as a
percent of average concentrations.
b
ALK error is the sum of error for all other cations and anions as
concentrations are not measured directly but rather are calculated using the
charge balance equation. An additional 5% uncertainty could be added here
for random error in the charge balance.
saturated valley bottom. In the uplands, soils are dark
colored, organic, and shallow (30 – 40 cm) in depth
overlying gently sloping bedrock. Within the valley bottom,
soils are >1 m in depth. Three soil water lysimeters along
transect T2 are located in the shallow organic soils of the
upland at depths of 30– 35 cm.
[18] All water samples were collected in 250 mL HDPE
bottles, filtered using 0.45 mm cellulose acetate syringe
filters, and separated for individual analyses. Samples were
analyzed for a suite of anions and cations, dissolved organic
carbon (DOC), and electrical conductivity (EC). Cation
samples were acidified to 2 – 3 pH and refrigerated at 4
C
until ion exchange chromatography analysis was performed.
Anion samples were frozen for storage purposes and thawed
for ion exchange chromatography analysis. Ion exchange
chromatography was performed at the University of Toronto
Mississauga geography department using a Dionex DX-
500. Electrical conductivity (EC) measurements were made
at 25
C on unfiltered sample water. DOC was measured
using a Shimadzu TOC 5050 organic carbon analyzer.
Analytical precision of measurements is expressed in per-
cent of average concentrations at the Lk (147 ha) catchment
for each solute (Table 2). Charge-balance alkalinity (ALK)
of each filtered sample was calculated assuming electrical
neutrality and by balancing the charges from all other major
ions [Kehew, 2001] where all other major ions were
measured directly using ion exchange chromatography.
Evaluation of analytical precision included analysis of
repeat samples to evaluate any changes in concentrations
due to extended refrigeration storage time (2 – 12 months).
3.2. Eigenvector and Residual Analysis
[19] We apply the diagnostic tools of Hooper [2003] to
estimate the number of end-members mixing to form stream
water. Using as input the catchment’s multivariate stream
water chemistry data set, an eigenvector analysis is per-
formed using the correlation matrix of the standardized
values. The analysis results is a series of eigenvectors that
reduce the dimensionality of the mixing space, transforming
a description of stream chemistry with dimensions equal to
the initial number of solutes (e.g., 9) to a lower dimension
(e.g., 2) with orthogonal axes describing the variance in
stream water chemistry. To objectively determine the di-
mensionality of the data set, or how many eigenvectors to
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W08434
retain, we apply residuals analysis for each solute [Hooper,
2003]. For an individual observation of stream water
chemistry, a residual is defined by subtracting the original
value from its orthogonal projection, the projection of the
original observation into the reduced dimensional mixing
space. Additional eigenvectors are retained until there is no
structure to the residuals [Hooper, 2003]. Dimensionality
determined by the residual analysis is compared with the
rule of 1, where each additional eigenvector retained should
explain at least 1/(number of solutes) of variance in the
stream chemistry [Joreskog et al., 1976]. The eigenvector
and residual analysis is first performed on the Lk catchment
(total outflow of 147 ha). The fit between observed values
stream water chemistry and their orthogonal projections is
evaluated using two measures of error [Hooper, 2003]. The
relative bias for solute j (bj) is a measure of the systematic
error between observed (xij) and projected values (^xij),
n 
P 
^xij
xij
bj ¼ i¼1 ; ð1Þ
n  xj
where xj is the mean of observations for solute j and n is the
number of observations. The relative root-mean-square error
(RRMSE) is the standard deviation between the observa-
tions and their projected values [Taylor, 1997] and is
normalized by the mean of the observations,
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u P n  2
u ^xij
xij
u
1
t i¼1
rj ¼ : ð2Þ
n xj2
[20] Similar analysis is performed for the seven addi-
tional catchments, allowing a comparison of mixing-space
dimensionality across scale. Stream water chemistry from
the seven additional catchments is projected into the Lk
catchment (147 ha) mixing model to evaluate the explan-
atory power of a single mixing model across scale and to
test the assumption of conservative behavior of geochem-
ical solutes.
3.3. Physical Interpretation of Contributing
End-Members
[21] In the physical interpretation of contributing end-
members, we attempt to integrate the eigenvector and
residual analysis of stream water chemistry with indepen-
dent sampling of potential end-members and field-based
hydrologic observations and site-specific knowledge. We
use the three criteria outlined by Hooper [2001] to identify
potential end-members. End-members must exhibit concen-
trations bounding that of the observed stream chemistry.
They must have lower variability than stream chemistry and
be distinct from other end-members [Hooper, 2001]. We
screen the independently sampled geochemical signatures
of end-members by projecting them into the mixing space of
the Lk (147 ha) catchment and evaluating the difference
between observed values and their orthogonal projections.
Ideally successful end-members will fit into the Lk mixing
space, bound stream water chemistry and support our
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE W08434

Figure 3. Piper diagrams of stream water chemistry for the Lk and Aw catchments and the natural
perennial spring (Seep). Sample sizes of stream water chemistry are included in Table 1.

conceptual understanding of how water moves to the stream
channel at MSH.
4. Results
4.1. Characterizing Stream Water Chemistry
[22] Stream water chemistry at MSH can generally be
classified as a mixed-cation bicarbonate facies where we
have used alkalinity (ALK) as a surrogate for bicarbonate.
Figure 3 illustrates Piper diagrams of stream water chemis-
try for the Lk (147 ha) and Aw (11 ha) catchments and the
natural perennial spring. At the Lk catchment, stream water
is a calcium-bicarbonate facies, with larger percentages of
Ca2+ than Mg2+ or (Na+ + K+) as shown in the bottom left-
6 of 17
hand triangle. The Aw catchment shows no single dominant
cation. The perennial spring water shows percentages of
cations that suggest borderline Mg2+ dominance. Here we
have assumed ALK can be used to approximate bicarbonate
concentrations, acknowledging that during storm events,
additional alkalinity may be added with increasing amounts
of organic anions from DOC [Wetzel and Likens, 1991].
[23] EMMA is a linear mixing approach and requires
tracers to exhibit conservative mixing, where geographical
sources of water (e.g., groundwater) of given geochemical
signatures physically mix together to form stream water.
This method is based on the assumption that stream water
chemistry is controlled by physical mixing and not by
equilibrium chemistry [Hooper, 2003]. Linear trends in
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE W08434

Figure 4. Bivariate solute plots of Lk catchment (147 ha) stream water chemistry, located at the outflow
of the Westcreek watershed (n = 123). Ions and ALK are in units of meq/L; DOC is in units of log (mmol/L);
EC is in units of mS/cm.

bivariate solute plots have been used to suggest conserva-
tive mixing of tracers [Christophersen and Hooper, 1992;
Hooper, 2003]. Figure 4 illustrates bivariate solute plots of
stream water chemistry from the Lk catchment (147 ha). We
observe a number of solute pairs to be collinear, exhibiting
strong linear trends (r2 > 0.5, p < 0.001) for Ca2+-Na+,
ALK-Na+, Mg2+-Ca, Mg2+-ALK, Ca2+-ALK. Weaker linear
trends (0.2 < r2 < 0.5, p < 0.001) are observed for Mg2+-


Na+, EC-Ca2+, EC-Na+, SO2
4 -NO3 solute pairs. Although
consistent with conservative mixing, linear trends in solute-
solute plots do not necessarily confirm conservative mixing
(R. Hooper, personal communication, 2004).
4.2. Independently Sampled End-Member Signatures
[24] Tracers included in EMMA must exhibit distinct
concentrations for potential end-members [Hooper et al.,
1990]. Figure 5 compares the characteristic geochemical
signatures of end-members as sampled from instrumentation
located along the two transects (T1 and T2) and the natural
perennial spring located immediate above the Sc gauging
station (Figure 1). Throughfall exhibits the most dilute
concentrations of base cations, ALK, and EC as compared
to other potential end-members. Riparian groundwater,
sampled from along the T1 transect of the upper Aw
catchment (T1 GW), offers the most dilute concentrations
from a terrestrial source of water. Mean concentrations at
the perennial spring (Seep) located lower in the catchment
system are slightly higher in both Ca2+ and Mg2+ concen-
trations than T1 groundwater (T1 GW), suggesting longer
contact time with bedrock and thus longer mean residence
times than for the upper Aw catchment local T1 groundwa-
ter. Perched water sampled along both the T1 (T1 PW) and
T2 (T2 PW) transects generally exhibits fairly high concen-
trations with, in some cases, significant spatial and temporal
variability. T1 soil water (T1 SW) collected from suction
lysimeters in mineral soils on the steep hillslope and the
valley bottom of transect T1 exhibits the highest Ca2+, Mg2+
concentrations and EC values when compared with other
end-members, including groundwater. Leaching of solutes
from the T1 hillslope potentially contributes to high con-
centrations observed in soil waters in the T1 valley bottom
where perched water can occur due to the local occurrence

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W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE W08434

Figure 5. Geochemical signatures of independently measured potential end-members. Boxes indicate

first to third quartiles, and whiskers indicate 10th and 90th percentiles. End-members include throughfall
(ThFall), groundwater (T1 GW, Seep), perched water (T1 PW, T2 PW), and soil water (T1 soil, T2 soil).
Ions and ALK in meq/L; EC in mS/cm; DOC in mmol/L.

of the shallow fragipan. This is likely due to the weathering of
plagioclase-feldspar [Tsujimura et al., 2001], a source of Ca2+
and HCO
3 ions in mineral soils of the hillslopes. Ca
2+
is the
base cation most susceptible to weathering, while other
cations may be stored in secondary minerals [Birkeland,
1999]. Under high storage (after spring snowmelt) or wet
antecedent moisture conditions, the perched areas in the
valley bottoms are connected directly to the stream channel.
As a result, high concentrations from soil waters provide a
possible upper bounding end-member to stream concentra-
tions of Ca2+, Mg2+, EC, and ALK.
[25] Sampling of T2 shallow organic soil water (T2 SW)
shows very different median concentrations than the T1 soil
water (T1 SW). The T2 location samples organic soils
immediately overlying bedrock without the thick underlying
mineral soil horizon of the T1 transect. Concentrations of base
cations in the T2 soil water are much more similar to T1
groundwater (T1 GW) and as a result do not offer a unique
signature. The T2 soil water does offer a unique DOC
concentration, the highest value beyond perched waters.
8 of 17
[26] Perched water from transect T1 (T1 PW) provides an
upper bound on Na+ concentrations that otherwise is not
accounted for by other potential end-members. This poten-
tial end-member also provides an estimated upper bound to
stream chemistry concentrations of ALK and DOC (with the
exception of the organic soil water) but not for base cation
(Na+, Mg2+, and Ca2+) concentrations. T1 riparian ground-
water (T1 GW) is surprisingly low in base cation concen-
trations as compared with the high concentrations of the T1
mineral soil water (T1 SW). Throughfall offers the most
dilute base cation, ALK, and EC concentrations and during
storm events could act as a lower bound to these solute
concentrations in the stream channel.
[27] On the basis of strong linear trends in the bivariate
solute plots and variation in end-member concentrations, we
include Na+, Mg2+, Ca2+, ALK, and EC as solutes in our
EMMA approach. Although DOC does help distinguish
end-members, and has been used in EMMA on an individ-
ual storm timescale, we do not include it here in the
seasonal time frame analysis. Instead we include DOC for
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE W08434

Table 3. Eigenvector Analysis for Individual Catchmentsa

Rank

Catchment 1st 2nd 3rd 4th 5th

Lk 72.8 14.7 (87.5) 6.7 (94.2) 3.8 (98.0) 2.1 (100)

Ef 87.3 6.1 (93.4) 4.4 (97.8) 1.6 (99.4) 0.6 (100)
Pw 72.2 17.1 (89.3) 7.2 (96.5) 2.3 (98.8) 1.2 (100)
Sc 72.2 14.8 (87) 6.7 (93.7) 4.7 (98.4) 1.6 (100)
Sb 64.1 27.5 (91.6) 4.0 (95.6) 2.7 (98.3) 1.7 (100)
Yv 58.9 17.6 (76.5) 14.6 (91.1) 7.4 (98.5) 1.5 (100)
Vc 71.8 15.7 (87.5) 8.5 (96) 2.8 (98.8) 1.2 (100)
Aw 71.8 20.0 (91.8) 6.1 (97.9) 1.7 (99.6) 0.4 (100)
Seep 73.3 15.2 (88.5) 9.2 (97.7) 1.8 (99.6) 0.4 (100)
a
Each column indicates the variance explained by each additional
eigenvector (1st, 2nd, 3rd, etc.) Numbers in parentheses indicate the
accumulated percent variance in stream water chemistry explained by
multiple retained eigenvectors. One hundred percent of variance is
explained for a rank of 5 (the total number of solutes included in our
analysis). With five solutes, the rule of 1 retains eigenvectors explaining
1/5th (20%) of variance (bold numbers).

analysis on an individual storm timescale as additional

independent evidence in the interpretation of contributing
end-members.
4.3. Evaluating Mixing-Space Dimensionality
[28] We estimate the dimensionality (or rank) of the
streamwater chemistry record at each catchment using as
inputs the five solutes: ALK, Ca2+, Mg2+, Na+, and EC.
With five solutes, the rule of 1 [Joreskog et al., 1976]
retains eigenvectors explaining 1/5th (20%) of variance. For
the Lk catchment, this results in a rank of 1, where two
contributing end-members explain a total of 72.8% of the
variance in stream water solute concentrations (Table 3). To
further evaluate mixing-space dimensionality, we examine
the residuals (xij
^xij) for each solute. Plotted against Figure 6. Residuals for Lk (147 ha) mixing space of one
observed concentrations (xij), a random pattern of residuals and two dimensions. Ions are in units of meq/L; EC is in
suggests a well-defined mixing model. If residuals are not units of mS/cm.
random, solutes may not adhere to the assumption of
conservative mixing or the model may require greater
dimensionality [Hooper, 2003]. Figure 6 illustrates residuals at 58.9% variance explained. For the Aw and Sb catch-
for individual solutes given an Lk (147 ha) catchment ments, three end-members (2-D mixing space) would ex-
mixing space of one and two dimensions. For all solutes plain over 90% of the observed variability. For the 1-D
except EC, the average magnitude of residuals is smaller or analyses of each catchment’s stream water chemistry, sta-
similar in value to the analytical precision (Table 2), tistical significant linear trends in EC residuals remain, often
resulting in no discernable pattern to residuals. This sug- because of the high concentrations observed during the
gests that the variance in these solutes is already well 16 June 2001 storm. For some catchments the linear trend
represented by mixing two contributing end-members. EC is weak, but in all cases the residuals are larger than the
is the only solute whose residuals pattern changes with an analytical precision (1.5 mS/cm) of the EC measurements
increase in dimensionality from one to two dimensions. In (Table 4), indicating structure or pattern. Two of the catch-
the case of EC, a small number of large stream water ments (Yv and Vc) also show residuals of alkalinity larger
concentrations provide large negative residuals. This small
number of high (>120 mS/cm) EC observations derive from Table 4. Linear Trends in EC Residuals for 1-D Mixing Spaces of
samples collected during a large storm (25 mm) on dry Individual Catchments (p  0.001)a
conditions on 16 June 2001. Retaining a second eigenvector
reduces these residuals to small values. Catchment r2 Mean Absolute Residual, mS/cm
[29] For each of the additional upstream catchments, an Ef 0.11 3.4
independent estimate of dimensionality is repeated using Pw 0.80 18.1
catchment-specific stream water chemistry. The rule-of-one Sc 0.48 7.4
Sb 0.55 2.7
estimates a rank of 1 (one-dimensional (1-D) mixing space) Vc 0.77 11.2
for all catchments with the exception of the Aw and Sb Yv 0.81 16.4
catchments, which have a rank of 2 (Table 3). For a 1-D Aw 0.92 9.6
mixing space, as with the Lk catchment, explained variance a
For all catchments, the mean absolute residual is larger than analytical
is quite high (>70%) with only the Yv catchment below this, precision of 1.5 mS/cm.

9 of 17
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE
Figure 7. Diagnostic statistics for fit of additional
catchment stream chemistry into the 2-D Lk (147 ha)
mixing space. Figure 7a shows the ‘‘at-site’’ RRMSE where
each catchment is projected into a 2-D mixing space created
by its own eigenvectors. Figures 7b and 7c show the
projected RRMSE and relative bias, respectively, for each
catchment projected into the Lk catchment 2-D mixing
space.
than analytical precision and statistically significant linear
trends. For the Yv (38 ha) catchment, r2 = 0.53, p < 0.001,
and the mean absolute residual is 230 meq/L compared
with analytical precision of 129 meq/L. For the Vc catch-
10 of 17
W08434
ment, r2 = 0.28, p < 0.001, and the mean absolute residual
is 180 meq/L. The residual analysis across scale suggests
a two-dimensional mixing space with three contributing
end-members.
[30] In Figure 7a, the ‘‘at-site’’ RRMSE evaluates the
variability of each catchment’s stream chemistry and the
ability of a catchment-specific linear 2-D model to explain
this variability where stream chemistry from each catchment
is projected into a 2-D mixing space created by its own
eigenvectors. At-site RRMSEs are similar across all catch-
ments with values ranging between 2 and 15% with only
one exception (ALK for catchment EF at 23%). This
indicates that a 2-D mixing-model specific to each catch-
ment gives high performance in explaining stream chemis-
try variability across space, as was indicated by the residual
pattern analysis and percent variance explained for a rank
of 2 in Table 3.
4.4. Projecting Upstream Observations Into the 2-D
Lk Mixing Space
[31] Using as reference the total outflow of the Westcreek
watershed, stream chemistry from the seven additional
catchments is projected into the 2-D mixing space of the
Lk (147 ha) catchment. Residuals for each catchment are
illustrated in Figure 8 and the corresponding diagnostic
statistics of projected RRMSE and relative bias, but are
described in Figures 7b and 7c, respectively. Projected
RRMSEs, where stream chemistry from each additional
catchment is projected into the 2-D mixing space of the
Lk (147 ha) catchment, can be compared to the at-site
RRMSEs (Figure 7a) described in section 4.3.
[32] The Ef catchment (91 ha), located immediately
upstream from the Lk catchment and delivering approxi-
mately two thirds of the total discharge, gives the best fit
into the 2-D Lk mixing space. The projected RRMSEs are
only slightly higher than at-site values, and the relative bias
(Figure 7c) is low for all solutes except Mg2+. In the case of
Mg2+, the positive relative bias indicates that stream water
concentrations are being overpredicted. These results indi-
cate that at the Ef catchment, solutes with the exception of
Mg2+ appear to be mixing with the same ratios as for the Lk
catchment.
[33] Upstream of the Ef catchment, fits deteriorate. The
residual analysis in Figure 8 indicates structure for solute
Mg2+ at all catchments upstream of Ef (91 ha) with perhaps
the exception of Sb (7 ha). Above the Ef catchment, Mg2+ is
underpredicted with the exception of the Sb catchment,
where we have a large overprediction of all solutes.
Figure 9 shows stream water chemistry observations from
all catchments for the Mg2+-ALK bivariate solute diagram.
Compared with the Lk stream chemistry, most of the
catchments exhibit higher Mg2+ concentrations with a lower
slope in the linear trend line. As a result, we observe
structure in Mg2+ residuals for many of the upstream
catchments.
[34] Upstream of the Ef catchment, Na+ and Ca2+ con-
centrations are consistently overpredicted by the 2-D Lk
mixing space. There is some pattern in Ca2+ for Sb (7 ha),
and Vc (11 ha) catchments and the perennial spring (Seep).
EC and ALK are generally better predicted across scale with
the exception of the Sb catchment. For the Sb catchment, all
solutes are overpredicted, indicating that stream water
chemistry is more dilute than the range of concentrations
 W08434

11 of 17
JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE

Figure 8. Residual analysis for additional seven catchments and the natural perennial spring (Seep) in the 2-D Lk
catchment (147 ha) mixing space. Ions are in units of meq/L; EC is in units of mS/cm.
W08434
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE W08434

observed at the Lk catchment used to create the 2-D mixing

Figure 9. Bivariate solute plot (ALK - Mg2+) of stream
chemistry. Stream chemistry at the Lk catchment (black
squares) is compared with that of the additional catchments
(grey triangles) and end-members. Symbols indicate the
median observed values end-members, and error bars
represent the 25th and 75th percentiles.
space.
4.5. Screening End-Members in the 2-D Lk
Catchment Mixing Space
[35] End-members are projected into the Lk (147 ha)
mixing space, testing their ability to fit in the mixing space
and to bound observed stream water chemistry. Using the
approach developed by Christophersen and Hooper [1992],
we compare the median values of end-members (lower
and upper quartiles in brackets) described in Figure 5 to
their orthogonal projections in the 2-D Lk mixing space
(Table 5). Criterion for an acceptable fit is set at 15%
difference between median values and orthogonal projec-
tions (bolded values).
[36] For EC and Ca2+, median throughfall concentration
shows 11% difference between observed and projected
values but percent differences are much larger for ALK and
Na+. The Lk mixing space predicts the median throughfall
Na+ concentration to be 83% higher, and the median ALK
concentration 78% lower than values sampled independently
in the field. Observed median Mg2+ concentration in
throughfall is also 23% higher than predicted. For riparian
groundwater sampled along transect T1 (T1 GW) all solutes
but Ca2+ show percent differences 11%, suggesting a good
fit in the Lk 2-D mixing space. The median perennial spring

Table 5. Median Observed Concentrations of Independently Sampled Potential End-Members, Orthogonal Projections in 2-D Lk
(147 ha) Mixing Space, and Percent Difference Between Projections and Valuesa
Solute Na+ Mg2+ Ca2+ EC ALK

Throughfall
Value 22 (20,31) 65 (26,68) 128 (96,196) 27 (22,40) 249 (170,315)
Orthogonal projection 35.7 61 140.7 22.8 50.9
Percent difference
84 23
13 5 74

T1 Groundwater (GW)
Value 111 (85, 144) 243 (171, 288) 354 (248, 461) 66 (53, 77) 640 (376, 809)
Orthogonal projection 102 220 443 52 567
Percent difference 10 9
38 2 4

Perennial Spring (Seep)

Value 99 (90, 112) 487 (389, 541) 427 (356, 469) 76 (70, 88) 842 (732, 943)
Orthogonal projection 135 322 599 60 875
Percent difference
30 34
42 17
3

T1 Perched Water (PW)

Value 510 (449, 601) 292 (265, 388) 406 (349, 505) 120 (102, 122) 1102 (1048, 1403)
Orthogonal projection 210 487 929 138 1439
Percent difference 61
83
176
35
30

T2 Perched Water (PW)

Value 80 (55, 107) 409 (297, 659) 531 (379, 674) 95 (72, 140) 1115 (809, 1539)
Orthogonal projection 173 396 767 92 1157
Percent difference
90 25
12 15
11

T1 Soil
Value 96 (90, 100) 793 (695, 868) 1918 (1506, 1973) 217 (210, 225) 1102 (868, 1295)
Orthogonal projection 259 579 1144 201 1784
Percent difference
170 26 33 7
65

T2 Soil
Value 84 (70, 101) 372 (254, 428) 328 (274, 366) 59 (43, 75) 619 (510, 733)
Orthogonal projection 121 265 537 84 724
Percent difference
3 28
31
8
17
a
Median values are accompanied by first and third quartiles in parentheses. Ions and ALK in meq/L; EC in mS/cm. Percent differences below 15% are in
bold, indicating a good fit in the mixing space.

12 of 17
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE W08434

(Seep) concentration shows larger percent differences for

Na+ and Mg2+. For both T1 GW and spring water, Ca2+
concentrations are approximately 40% lower than pre-
dicted by the Lk 2-D mixing space.
[37] T1 perched water (T1 PW) does not fit well into the
Lk mixing space for any of the five solutes. The median
field sample is too high in Na+ (61% higher) and too low in
other solute median concentrations compared with orthog-
onal projections. However, T2 perched water (T2 PW) fits
fairly well into the mixing space for Ca2+, EC, and ALK.
The median concentration values are 25% higher than
predicted for Mg2+and too low in Na+ (
90%). T1 soil
water (T1 SW) is a poor fit with absolute differences
ranging from 21 to 172%. T2 soil water provides a fair fit
(values only slightly above the 15% fit criterion in some
cases) albeit too high in Mg2+ (28%) and too low in Ca2+
(
31%). Generally, greater success for independently sam-
pled end-member fitting into the 2-D mixing space is
observed for solutes EC and ALK, suggesting that the
assumption of conservative behavior is most appropriate
for these two solutes.
[38] End-members must also bound observed stream
water chemistry. Figure 9 shows perched water from
transect T2 (T2 PW) providing a high concentration end-
member for ALK and Mg2+ concentrations, while ground-
water (T1 GW) and throughfall (Thfall) offer are more
dilute end-members. For lower-concentration stream water,
T2 soil water (T2 SW) is in line with the upper bound of
Mg2+ concentrations. All four of these end-members show
some consistency with the 2-D Lk mixing space. Symbols
indicate the median observed value end-members, and error
bars represent the 25th and 75th percentiles.
[39] Figure 10 illustrates the 2-D Lk mixing space or
Uspace, where U1 and U2 are orthogonal axes derived from
the principle component analysis. In Figure 10a, stream
water chemistry from the Lk (147 ha) catchment only is
represented by black circles while in Figure 10b all stream
water chemistry is included (n = 842). Projected values of
end-members represent average observed values from indi-
vidual instruments (e.g., wells, piezometers, lysimeters),
data used in the calculation of the median value of each
end-member represented in Table 5. Groundwater (T1 GW,
pink circles) clearly bounds stream water concentrations on
the negative U1 axis. For this timescale of analysis, where
multiple field seasons of observations are included, through- Figure 10. Lk (147 ha) 2-D mixing space or Uspace:
fall is not a unique bounding end-member, located to the (a) Lk stream water chemistry only and (b) stream water
right of groundwater (T1 GW) on the U1 axis. Observations chemistry from all catchments. Projected values of end-
of perennial spring water (Seep) show an evolution in members represent average observed values from individual
concentrations (see also Figure 9), providing an upper instruments (e.g., wells, piezometers, lysimeters). These
positive bound along the U2 axis. Under later-spring wet data are also used in the calculation of the median value of
conditions, T1 GW and Seep concentrations overlap on the each end-member represented in Table 5.
U1 axis, while later in the season, these end-members
diverge in geochemical signatures. Individual observations catchment, although each end-member could certainly be
of perched water (T2 PW) show large variability but suggest contributing to varying degrees in space. The rule of 1
a bounding end-member along the positive U1 axis. provides variable estimates of catchment dimensionality,
supporting a 2-D mixing space for two of the eight catch-
5. Discussion ments and a 1-D mixing space for the remaining six.
5.1. Stream Water Mixing-Space Dimensionality However, residual analysis suggests a rank of two or three
contributing end-members for all catchments based on
[40] We hypothesize that all catchments should display linear trends in EC residuals and in two instances, alkalinity
the same dimensionality or rank. This is based on the residuals. This analysis appears to support our hypothesis
assumption that all end-members are present in any given of similar rank across scale. The small number of high

13 of 17
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE
(>120 mS/cm) EC observations in stream water chemistry
derives from samples collected from all catchments during
a large storm (25 mm) on dry conditions on 16 June
2001. In contrast, water sampled from the natural peren-
nial spring during this storm event does not show these
high fluctuations, supporting the interpretation that during
this storm an additional end-member is contributing to the
stream channel.
[41] In this study, stream water was sampled over two
late-spring to early-fall field seasons and focused specifi-
cally on 12 storm events, resulting in sample sizes ranging
from 50 to 129 depending on the catchment (Table 1). In
comparison, the analysis performed on the Panola Mountain
Research Watershed [Hooper, 2003] had over 223 data
points for each gauging station and in two cases samples
sizes >1000. Our focus on sampling of storm events under
varying antecedent moisture conditions optimizes the chan-
ces of representing contributing end-members in this
smaller data set. However, a greater sample sizes could
provide additional evidence for a 2-D mixing space. Future
collection of additional data and the following discussion of
hydrologic interpretation provide a way forward to substan-
tiate the rank of stream water chemistry at MSH.
5.2. Comparison of Stream Water Chemistry Across
Scale
[42] The projection of stream water chemistry from the
upstream catchments into the Lk 2-D mixing space allows
us to compare variation in stream water chemistry across
scale and attempt to examine where and for what solutes
does control by physical mixing apply. For instance, our
analysis indicates that Na+, Mg2+ and Ca2+ either (1) do not
adhere to the assumption that concentrations are being
controlled by physical mixing or (2) are not mixing with
the same ratios upstream of the Lk gauging station. The at-
site RRMSEs for these three solutes are fairly low for all
catchments, suggesting that they do adhere with physical
mixing control and the linear mathematics in a catchment-
specific 2-D mixing space. The projected RRMSEs and
relative bias, though, can be quite large, indicating that the
mixing ratios of ions are changing upstream of the Lk
catchment. The Sb and Aw catchments provide strong
examples of this, with large projected RRMSEs and relative
bias for Na+ and Ca2+ (Figures 7b and 7c). In the case of
Mg2+, we observe the relative bias shift from overprediction
(positive relative bias) to underprediction (negative relative
bias) of values depending on the catchment.
[43] Compared with the other solutes, ALK and EC
generally offer smaller and more consistent projected
RRMSE and relative bias across scale. This suggests ALK
and EC are more appropriate solutes for use in a single
linear mixing model application across scale. The large
relative bias and projected RRMSE for the Sb catchment
results from more dilute concentrations compared with
those observed at the Lk catchment. The Sb catchment is
ephemeral, and observations of stream water chemistry are
generally only possible under high storage (wet) conditions
such as during late-spring/early-summer time periods. Dur-
ing this time, stream water chemistry at MSH is generally
more dilute than later in the season. However, Sb concen-
trations are still more dilute than those observed at the Lk
catchment. Solute plots of Sb stream chemistry still indicate
14 of 17
W08434
a linear pattern, simply extending the lower range of
concentrations observed at the Lk catchment.
[44] The spatial variation in stream water chemistry may
be a function of the spatial variation in bedrock and soil
composition, which will affect the geochemical signature of
the groundwater end-member in particular. Chemical anal-
yses of bedrock samples performed by Currie [1983]
indicate varying MgO and CaO concentrations in the two
suites (Sunrise and Pain de Sucre) dominating the western
side of MSH, with higher concentrations of both oxides in
the Sunrise suite (Figure 2). Groundwater contact with
variation in bedrock composition could result in spatial
variation of mixing ratios. There is also evidence of pockets
of thick glacial till that could also provide spatial variation
in geochemical signatures. In the Aw catchment, a 5-foot-
thick (1.52-m) layer of glacial tile (or mineral soil) overlies
steep sloping bedrock on the west side of the catchment in
contrast to only shallow organic soils on the eastern side.
Geochemical sampling of the mineral soil from transect T1
(T1 soil) offers significantly different geochemical signa-
tures as compared with the organic soils overlying bedrock
(T2 soil). The presence of localized pockets of glacial till is
also supported by the variable gaining-losing reaches of the
stream channel and the presence of the natural perennial
spring. Although both the Sb and Yv catchments were
observed to be ephemeral, immediately below these two
gauging stations, the natural spring provides continuous
flow, suggesting losses immediate upstream to a permeable
reservoir that is expressed at the spring. Clearly the bedrock
geology at MSH is complex and the distribution and
minerology of glacial tile is relatively unknown. Further
quantitative spatial analysis would be required to explicitly
attribute changes in stream water chemistry to bedrock and/
or soil maps.
[45] The 2-D Lk mixing model is most successful at
predicting stream water chemistry at the Ef (91 ha) gauging
station located at the convergence of the east and west forks
of the Westcreek watershed stream system 20 m upstream of
the Lk gauging station. At this station, Mg2+ is overpre-
dicted but the remaining five solutes show small relative
bias and fairly small projected RRMSEs (Figure 7b). The
capacity of the mixing model to predict stream water
chemistry for the two largest catchments is suggestive of
a naturally occurring representative elementary area (REA),
a scale at which there is reduced variability in hydrologic
response and above which resolution of the pattern of local
heterogeneity is not necessary [Wood et al., 1988]. Similar-
ity in stream water chemistry at the Ef and Lk catchments
suggests an REA of 0.9 km2. In comparison, Wolock et al.
[1997] observed solutes concentrations (e.g., acid neutral-
izing capacity, sum of base cations, pH, aluminum, DOC,
silica) to stabilized at approximately 3 km2 within the
Neversink River watershed in New York State, interpreting
this as the area required to attain equilibrium with the
hydrologic and geologic system.
5.3. Hydrologic Interpretation of Source Water
Contributions
[46] The eigenvector and residual analysis of stream water
chemistry and the screening of independently sampled end-
members provide evidence against which to test our current
understanding of hydrology at MSH. Independent sampling
of groundwater is successful in fitting into the 2-D Lk mixing
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE
Table 6. Seasonal Changes in Base Flow and Groundwater Concentrations: Spring – Fall 2002
Solute Lk Catchment Base Flowa D [ ] Perennial Spring D [ ]
Na+, meq/L 98
Mg2+, meq/L 324
Ca2+, meq/L 568
EC, mS/cm 39
ALK, meq/L 888
a
Maximum difference in base flow concentrations during spring to fall 2002.
b
Maximum range observed from wells and piezometers in transect 1 (T1). Average of three instruments with maximum change in brackets. Observations
taken from 4 June to 1 November 2002.
space and bounding stream water chemistry. However, we
observe a strong seasonal evolution of the chemical signature
of the perennial spring (Seep, Figures 9 and 10) and a
corresponding evolution in stream water solute concentra-
tions attributable to the occurrence of spring snowmelt
[Kendall et al., 1999] and the mixing of different age
reservoirs of groundwater. At MSH, water from spring
snowmelt mixes with preexisting groundwater and soil water
resulting in relatively dilute groundwater solute concentra-
tions. Concentrations increase over the growing season
(Table 6). For example, over the course of the 2002 spring-
fall season, ALK concentrations increase by 536 meq/L in the
perennial spring, and by 888 and 463 meq/L in stream water
from the Lk and Aw catchments, respectively.
[47] This seasonal change in spring and base flow geo-
chemistry in catchments controlled by snowmelt mixing
[Kendall et al., 1999] has been positively correlated with
seasonal increase in mean contact or residence time of
groundwater. Positive correlation between residence time of
spring water and concentrations of base cations related to
mineral weathering (Ca2+, Mg2+, Na+) has been found for
springs in the Sierra Nevada [Rademacher et al., 2001]. On
timescales greater than a single storm event (e.g., seasonal or
multiple-year), solute concentrations, particularly major base
cations (e.g., Ca2+, Mg2+, Na+, K+) are often monitored
as nonconservative tracers [Ogunkoya and Jenkins, 1993;
Elsenbeer et al., 1994; Wolock et al., 1997; Burns et al., 1998;
Rice and Hornberger, 1998; Kendall et al., 1999], reflecting
contact time or residence time because of slow mineral
dissolution rates [Lasaga, 1984]. The greater the contact (or
residence) time, the larger the tracer concentration until some
maximum steady state value is attained [Trudgill et al., 1996;
Burns et al., 1998]. Base flow will likely exhibit a maximum
tracer concentration due to long residence time in the catch-
ment system [Trudgill et al., 1996]. The time evolution of the
geochemical signature of groundwater conflicts with the
assumptions of end-member mixing analysis where signa-
tures must be constant for the travel time of water from
geographical sources to the stream channel.
[48] An alternative interpretation would be to consider
groundwater with its changing geochemical signature to be
a mixture of reservoirs [Rademacher et al., 2005]. In the
case of the MSH analysis, we could assume groundwater
(e.g., Seep) to be a mixture of two time-invariant reservoirs,
a young (dilute) and old (concentrated) groundwater phys-
ically mixing to form groundwater contributing to the
stream channel. For a seasonal or multiyear timescale
analysis of stream water at MSH, these two groundwaters
appear to be necessary end-members.
[49] In section 2.2 we hypothesized that the transient
formation of perched water in the valley bottoms occurs
W08434
T1 Groundwaterb D [ ] Aw Catchment Base Flowa D [ ]
39 18 (58) 24
389 136 (211) 234
232 304 (442) 283
28 20 (38) 35
536 471 (849) 463
due to the presence of the shallow fragipan and potentially
expresses itself in the stream channel as a contributing end-
member. The analysis presented in Table 5 and Figure 10
supports this hypothesis showing fit for perched water but
not for T1 soil water, sampled from a pocket of glacial till
along the T1 transect. We believe the high cation concen-
tration of T1 soil water is a function of the presence of
localized glacial till on the western side of the T1 transect.
We suspect that this till is variable in its presence, contrib-
uting the high localized concentrations along transect T1
and possibly to the varying mixing ratios of Mg2+ and C2+
observed across scale. Groundwater solute concentrations
from the Aw catchment are generally lower than these
observations, indicating an overall dilution of solute con-
centrations at the scale of the catchment.
[50] Figure 11 illustrates response of stream water chem-
istry to a 38 mm storm event under dry conditions. In
Figure 11a, tracers of dissolved organic carbon (DOC) and
d18O illustrate the bounding of stream water chemistry by
contributing end-members of groundwater, throughfall and
perched water providing further support for our hypothesis
of a perched water end-member. Figure 11b illustrates a 2-D
mixing space (Uspace) created by eigenvector analysis of
stream water chemistry from all catchments during this
single storm event. In this analysis, EC, ALK, and DOC
were used as tracers. Results from this single-event analysis
help inform the analysis using the entire two-season stream
water chemistry record. Although average solute observa-
tions of groundwater, throughfall, and perched water offer
good fits within this 2-D mixing space, soil water does not,
with percent differences between observed and projected
values of solutes of
41,
37, and 54% for EC, ALK, and
DOC, respectively. The evolution of stream water chemistry
during this storm is illustrated for three catchments (Lk, Aw,
and Vc). Stream water appears to begin as a mixture of
groundwater and perched water, shifting toward throughfall
along the U1 axis during the storm, and for some catch-
ments, rising on the U2 axis toward perched water before
returning toward its starting point. The difference in the
expression of perched water in different catchments is
illustrated by the Vc catchment, where the gauging station
of this catchment is connected to transiently formed perched
water within a low-lying area located immediately up-
stream. The individual storm event analysis provides addi-
tional support for a perched water end-member.
6. Conclusions
[51] The eigenvector and residual analysis of the multi-
variate MSH data set supports a 2-D mixing space for all
eight variably nested catchments. On an individual catch-
15 of 17
W08434 JAMES AND ROULET: APPLICABILITY OF EMMA ACROSS SCALE
Figure 11. Response of stream water chemistry to a 38 mm storm event: (a) DOC versus d18O;
(b) storm-based 2-D mixing space or Uspace.
ment basis, a 2-D linear mixing-model provides good
results in explaining variation in stream water chemistry
for the five selected solutes. However, when upstream
observations from the seven additional catchments were
projected into the 2-D mixing space of the Lk (147 ha)
catchment, the overprediction or underprediction of solute
concentrations indicate a failure in the mixing model
assumptions. Although Mg2+, Ca2+, and Na+ appear to be
good candidate solutes for conservative mixing, showing
linear trends in bivariate solute plots (Figure 4) and showing
distinct concentrations in end-members (e.g., T1 soil and
perched water in Figure 5), our analysis indicates that they
do not mix in the same ionic ratios in all catchments. The
changing mixing ratios Mg2+ and Ca2+ may result from the
complex bedrock geology and pockets of glacial till vari-
ably distributed throughout the Westcreek watershed. Ad-
ditional spatial analysis could provide a quantitative
examination of the relationship between spatial patterns in
stream water chemistry and bedrock and soil mineralogy.
The similarity in mixing at the Ef (91 ha) and Lk (147 ha)
catchments is suggestive of an approximate representative
elementary area (REA) of 0.9 km2. In this analysis we were
unable to a priori determine appropriate conservative trac-
ers. Only the spatial testing of upstream catchment stream
water chemistry in the Lk mixing space identified ALK and
EC as most compatible with the application of a single
mixing model across scale.
[52] Independent sampling of source waters was success-
ful in identifying end-members that fit in the 2-D Lk
(147 ha) catchment mixing space and bound stream water
observations. The physical interpretation of contributing
end-members varies somewhat with the timescale of anal-
ysis. On the timescale of a spring-to-fall season, the
physical mixing of two groundwater end-members, one
young in residence time with relatively low solute concen-
16 of 17
W08434
trations and one old in residence time with high solute
concentrations, is required to account for the seasonal
changes in geochemistry of groundwater. A perched water
is proposed as a third end-member. For the timescale of an
individual storm event observed on dry summer conditions,
we assumed groundwater to be a single, well-mixed reser-
voir. In this case, analysis suggests stream water is a mixture
of groundwater, perched water, and throughfall.
[53] Acknowledgments. The authors would like to thank Raissa
Marks, Sheena Pappa, Catie Burlando, and Nathan Deustch for their tireless
assistance in the field and the staff of the Mont Saint-Hilaire nature reserve
for their logistical support. Thanks also to Brian Branfireun, Carl Mitchell,
and fellow students for ion exchange chromatograph analysis at University
of Toronto, Mississauga. The authors benefited from discussion with
Richard Hooper on EMMA, PCA, and dimensional analysis. Bob White-
head and Doug Goldsack provided helpful discussions on geochemistry and
principal component analysis. Thanks also to Jake Peters for an early
reading of the manuscript and to Doug Burns and two anonymous
reviewers for detailed and constructive reviews. This work was funded in
part by the National Sciences and Engineering Research Council of Canada
(NSERC), a McGill-McConnell Fellowship, a McGill Graduate Studies
Fellowship, and the McGill Global Environment and Climate Change
Centre (GEC3).
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A. L. James, Department of Forest Engineering, Oregon State
University, 204 Peavy Hall, Corvallis, OR 97331, USA. (april.james@
mail.mcgill.ca)
N. T. Roulet, Department of Geography, McGill University, 805
Sherbrooke Street West, Montreal, Quebec, Canada H3A 2K6. (nigel.
roulet@mcgill.ca)