WATERRESOURCES

RESEARCH,
VOL.34,NO.1,PAGES129-137,
JANUARY1998

Causes of concentration/dischargehysteresis and its potential

as a tool for analysis of episode hydrochemistry
Christopher
EvansandTrevorD. Davies
Schoolof EnvironmentalSciences,Universityof East Anglia, Norwich,England,United Kingdom

Abstract. Episodicvariationsin dissolvedsolutesare frequentlycomplicatedby a cyclical

relationship
betweenconcentration
andstreamdischarge.
Established
three-component
modelsof runoff generationare usedto explainthis hysteresis effect and to illustratehow
differentcomponentconcentrations producedifferenthysteresis forms.It is demonstrated
that a two-componentmodel cannotreproduceall the hysteresisforms commonly
observed.A method, basedon the three-componentsystem,is derivedby which C/Q
hysteresiscan be usedto predictrelativecomponentconcentrations. This may providea
qualitativechemicaldescriptionof sourcessupplyingrunoff for locationswhere thesehave
not yet been directlyestablishedor a validationtest where possiblecomponentshave been
sampled.The methodhasbeen testedusingdata collectedat streamsin the Adirondacks,
New York, and the Northern AppalachianPlateau, Pennsylvania,during the Episodic
ResponseProjectof the U.S. EnvironmentalProtectionAgency.Predictedcomponent
compositions were in good agreementwith measurementsmade during other studiesand
with thosesubsequentlyobtainedfrom one of the Pennsylvaniawatersheds.

1. introduction U.S. EnvironmentalProtectionAgency'sEpisodicResponse

Much of the chemical variation in streamwater occurs in
responseto periodsof increaseddischarge.However, despite
therefrequentlybeinga clearresponseof concentration(C) to
discharge(•), this rarely takesa simplelinear or curvilinear
form [Wallingand Webb,1986].Hendricksonand Kreiger[1964]
and Toler [1965] observedcyclicalrelationshipsbetweendis-
chargeandconcentration of dissolved solids,wherebythe con-
centrationat a givendischargeon the risinglimb of the hydro-
graph differed from that at the samedischargeon the falling
limb. This hysteresisin the episodeC/Q relationshiphassince
been observedby numerousauthorsin the United Kingdom
[Oxley,1974;Johnson andEast,1982;Wallingand Webb,1986],
Norway [Johannessen et al., 1980] and U.S. [Millerand Drever,
1977;Bond,1979;Swistock et al., 1989;Hooperet al., 1990;Hill,
1993;Shanleyand Peters,1993].
C/Q hysteresisoccurswheneverthere is a differencein the
relative timing or form of solute and dischargeresponses
[Wallingand Webb,1986].Wallingand Foster[1975] suggested
that observedhysteresis(in the form of laggedsolutere-
sponses)mightbe dueto the earlyepisodeflushingof soluble
material. It has sincebeen recognizedthat hysteresiscan also
resultfrom componentmixingprocesses [Swistocket al., 1989;
Hooperet al., 1990]. This studywill use a simplemodelling
approachto examinethe relationshipbetweencomponentmix-
primarilyin terms of the three- [1994],Jenkinse! al. [1994],and Elsenbeeret al, [1995a].All of
ing and C/Q hysteresis,
componentmodel(3CM). An assessmentwill alsobe madeOf thesestudiesconsidergroundwater/baseflow and mineral soil
the extentto whichthe simplertwo-component model (2CM)
can generatethe sameresults.Methods are developedwhich
relate the form of a hysteresisloop to the relative concentra-
tion of different sourcecomponents,and theseare testedusing
data collected at streams in the Adirondacks, New York, and
the Northern AppalachianPlateau, Pennsylvania,during the
Copyright1998by the American GeophysicalUnion.
Paper number97WR01881.
0043-1397/98/97WR-01881509.00
129
Project(ERP) [Wigington
et al., 1996].The ERP includedin-
tensive episodic streamwater sampling but did not monitor
possiblesourcecomponentssuchas soil water or throughfall.
A method for predicting component compositionsusing
stream data would thus be a valuable addition to this study.
Resultsare comparedwith thosefrom other studiesand with
the results of recent samplingof one of the original ERP
streamsto assesswhether the methodsdevelopedprovide re-
alistic results.
2. Methods
2.1. Modelling Runoff Using a Three-ComponentSystem
The 2CM generallyconsiders"event"and "pre-event"water
sources.Event water usually equates to precipitation or
throughfall,with pre-eventwater representingstored subsur-
face water of uniform chemical/isotopic composition.How-
ever, in systemswhere water from the soil zone makesa sig-
nificant and chemically/isotopicallydistinct contributionto
runoff, it is necessaryto considerthis as a third component
[Kennedye! al., 1986;DeWalle e! al., 1988a].A number Of
studieshave employedsomeform of 3CM, includingthoseof
DeWalle et al. [1988a], Swistocket al. [1989], Hooper et al.
[1990],McDonnellet al. [1991],Ogunkoya and Jenkins[1993],
Hinton
e!al.[1994],
Bazemore
e!al.[1994],
DeWalle
andPionke
water components.In most casesthe third componentcan be
looselydefinedas"surface
event"Water,consisting
of di.rect
channelinterceptionand/or saturationoverlandflow (SOF).
This is commonlyassumed
to retainthe composition
of pre-
cipitationin grasslandcatchments or of throughfallin forested
basins,although chemicalinteractionwith surficialmaterials
hasbeen shownto occurduringoverlandflow by Hill [1993]
andElsenbeer et al. [1995b].Elsenbeeret al. [1995a]measured
SOF to represent surface event water, while Hooper et al.
[1990]identifiedorganicsoilwater as a third component.
130 EVANS AND DAVIES: CONCENTRATION DISCHARGE HYSTERESIS

--o- Surface event water

---n-- Soil water
-•- Groundwater

-•- TotalDischarge

m 15

• lO

0 1 2 3 4 5 6 7 8 9 10

Time from start of episode(arbitraryunits)

Figure 1. Syntheticepisodehydrographusedto model C/Q loops.

For a 3CM of groundwater,soil water, and surface event Elsenbeeret al. [1995a],timingsfor these components were
water components, the concentration of a conservative solute actuallyreversed.However,the assumedprecedenceof surface
in streamwaterat a given time is describedby the following eventwater is consistent with the variablesourceareaconcept,
massbalanceequation: in that flow from direct precipitation onto saturated areas
peaksbefore subsurface flow [Dunneand Black, 1970;Hewlett
C•Q• = CoQo + CsoQso+ Cs•Qs• (1) and Nutter, 1970]. This systemis likely to operatewidely in
where C is concentration,Q is discharge,and the subscripts T, humid forestedbasins.It alsoseemsreasonableto expectsoil
G, SO, and SE representtotal streamflow,groundwater,soil water responseto be lagged,giventhat a large proportionis
water, and surfaceeventwater, respectively.The methodsde- likely to derive from hillslope areas, away from the stream
veloped here require only that C•: and Q•: are measured. network, and that conditionsof saturationmust usuallyde-
Provided an event follows a period of low flow, Ca can be velop (becauseof either a risingwater table or the develop-
approximatedby the pre-eventC•:. Three-componenthydro- ment of perchedsaturation)before significantflow can occur
graphseparationsrequiremeasurementOf the two "stormflow [Lynchand Corbett,1985;Swistocket al., 1989;Hooperet al.,
components,"C so and C SE, but these are treated here as 1990].Groundwaterdominanceis consistentwith ridgingthe-
unknowns.Sincecomponentdischargesare alsounmeasured, ories[SklashandFarvolden,1979;Gillham,1984]or a simpler
precisevaluesfor C so and CSEcannotbe calculated.However, mechanismof old water displacement.The sensitivityof the
by makingcertainassumptions regardingthe natureof hydro- model to changesin assumptions is consideredbelow.
graph response,it is possibleto obtain estimatesfor C so and A simpleconceptualthree-component hydrograph,basedon
C SE relative to Ca and to each other so as to determine this flow model, is shownin Figure 1. The hydrographis the
"componentrankings." hypotheticalresponseto a single-peaked rain input. This was
An empiricallybased runoff sequenceis assumedfor this used to generate a set of C/Q plots based on a range of
study.It is essentiallythat describedfor MahantangoCreek, different componentconcentrations.Componentswere as-
Pennsylvania,
Wherea typicalprogression during signedconcentrationsof 50, 100, and 150 arbitraryconcentra-
of dominance
stormflowis believedto be (1) baseflow, (2) channelprecipi- tion units in a total of sixpossiblecombinations.
tation and SOF (surfaceeventwater), (3) shallowsubsurface
flow (soilwater), and (4) baseflow [Pionkeet al., 1988;DeWalle 2.2. Interpretation of C/Q Plots
andPionke,1994].Other studiesin Pennsylvania by Swistock
et C/Q plots for each combinationof componentconcentra-
al. [1989]andFulcar [1990]haveobservedthe samesequence, tionsare shownin Figure 2. It is apparentthat eachcombina-
as have Hinton et al. [1994] for a June event at Harp 4-21, tion producesa distincthysteresis loop. Clockwiseloopsare
Ontario.SklashandFarvolden[1979]foundtwo components to classedas typesC1, C2, and C3, and anticlockwise loopsare
be sufficientfor streamsin Quebec and Ontario but predict classedastypesA1, A2, and A3. From (1), CT at a giventime
that in a three-componentsystem,eventwater would be most will tend towardsthe flow componentwhichdominatesat that
important on the rising limb and vadose soil water on the time. At base flow, CT is by definition equal to Ca; on the
falling limb. Consistentwith theseand other studies,ground- risinglimb it tendstowardsC SE,andon the fallinglimb it tends
water responseis assumedto be large and (as a result of its towardsCso. If, for instance,CSE> Ca > Cso, CT will peak
overalldominance)closelycorrelatedto total discharge. on the risinglimb and reach a minimumon the falling limb,
It is acknowledged that this model may not be universal:at generatinga type C1 loop.The oppositesituation(Cso > Co
Allt A'Mharcaidh, Scotland,Q sE and Q so peakstend to co- > CSE) will produce the equivalentA1 type anticlockwise
incide[Ogunkoya andJenkins,1993;Jenkinset al., 1994],andin loop. If C SEand C so are both either higheror lowerthan Ca,
one of two eventsmonitoredat South Creek, Queensland,by that is, Ca is "extreme"rather than "intermediate,"one limb
 EVANS AND DAVIES: CONCENTRATION DISCHARGE HYSTERESIS 131

(a) C 1 (CSE> CG > Cso) Co)c2 (CsE> Cso > Co) (c) C3 (CG > CSE> Cso)

110
• 70
• 140
._•130
• '•2o

• 70 I • 40 0 20
i
40
c•11o 0 20 i
40
0 20 40
Discharge(arbitraryunits) Discharge (arbitraryunits)
Discharge(arbitraryunits)

(d) A1 (Cso > Ca > CSE) (e) A2 (Cso > CSE> Ca) (f) A3 (Co > Cso > CSE)

•' 80

110 • 70
100 130
120

80
0
I
2o
' I
4o
• 40 0 20
i
40

Discharge(arbitraryunits)
110
0 2040 Discharge (arbitraryunits)
Discharge(arbitraryunits)

Figure 2. C/Q hysteresisloopscreatedusinghydrographin Figure 1.

becomespartiallyconcave.This occursbecauseboth risingand where a loop is concave.A positivetrend implies that CT is

falling limbs tend away from the baseflow value.
Given that each combinationof componentconcentrations
producesa distinctand recognisablehysteresisloop, it is pro-
posedthat where theseforms are observedin real C/Q plots,
certain predictionscan be made regardingunknown compo-
nent concentrations. Three basic criteria are needed to char-
acterisethe varioushysteresistypes.
1. Rotational pattern (clockwise/anticlockwise). In any
event for which the three-componentconcentrationsdiffer, a
hysteresisloop will occur which can be either clockwiseor
anticlockwise.In a clockwiseloop CT is higher on the rising
limb than on the fallinglimb. CSEmustthereforeexceedCso.
With an anticlockwiseloop C so must exceedC SE.
2. Curvature(convex/concave). Technically,all loopsmust
be primarily convex.Here, however,the term is taken to mean
that the entire loop is convex.On this basisa "convex"loop
impliesthat on one limb, CT musttend towardsa valuegreater
than Co, and on the other to a value lessthan Co. Thus Co
must be intermediaterelative to the other components.Fol-
lowingthis definitionof convexity,a "concave"loop is one in
which all or a significantpart of one limb is concave.As
discussedabove, this implies that Co must have either the
highestor lowestcomponentconcentration.
3. Trend (positive/negative). This needonlybe considered
consistentlyhigherduringthe eventthan it is at baseflow, and
hence that Co has the lowestconcentrationof the three com-
ponents.A negativetrend impliesthe opposite,that is, that CG
has the highestconcentration.
Thesediagnosticfeaturesare togethersufficientto placethe
episodicbehaviorof a givensoluteinto one of six categories.
Each has a unique set of componentrankings,as shownin
Table 1.
2.3. Hysteresis in a Two-Component System
To someextent,the hysteresis
formsobservedusinga 3CM
can also be generatedby a 2CM; in this case,pre-eventand
event water sourcesare considered, but the observationsmade
are applicableto any two components.For a systemin which
event water peaks before pre-event water, CT will be most
different to its base flow value on the rising limb. It is thus
possibleto generatehysteresistypesC2 and A3 as shownin
Figure2. If eventwater is laggedbehindpre-eventwater, types
C3 and A2 can be produced.Componentrankingsfor a pre-
event/event water 2CM are included in Table 1.
Two-solutemixing plots have previouslybeen used to dis-
tinguishbetweentwo- and three-component systems[e.g.,De-
Walle and Pionke, 1994]. Deviation from a straight"mixing
line" impliesa need for a third component.The two systems

Table 1. DiagnosticFeaturesUsed to Determine ComponentRankings

ComponentRankings
Rotational
Type Direction Curvature Trend 3CM 2CM

C1 clockwise convex N/A C SE > C O > C so N/A

C2 clockwise concave positive CsE > C G > CG CEVENT> CpRE_EVEN
T
C3 clockwise concave negative Ca > CSE > Cso CpRE_EVEN
t • CEMEN
T
A1 anticlockwise convex N/A Cso > Ca > CSE N/A
A2 anticlockwise concave positive Cso > CE > Ca CEMENT • CpRE_EVEN
t
A3 anticlockwise concave negative Ca > Cso > CSE CpRE_EVENt • CEMEN
T
132 EVANS AND DAVIES: CONCENTRATION DISCHARGE HYSTERESIS

130
plot will be intermediatebetweenconvexand concaveforms,
so that part of the loop becomeslinear (e.g., Figure 3b).
An increasein the magnitude of either Q SE or Q so will
110
causeCT to tend more towardsthe concentrationof that com-
ponent,especiallyon the limb where it dominates.An elevated
80%
proportionof flow from Q o will reducethe amountby which
CT deviatesfrom its pre-eventvalue, resultingin the "stretch-
ing" effect shownin Figure 4. Significantly,no changein com-
ponent dischargemagnitudewill affect basicshapecharacter-
istics,or subsequentinterpretation,in any way. Although a
"large"groundwaterresponsewas assumedin the model used,
0 10 20 30 40 then, the exactmagnitudeof Q o is unimportant.
Discharge(arbitraryunits) The hydrographmodel usedassumesthat QSEpeakson the
risinglimb, Qo peaksat or closeto maximumQT, and Qso
Figure 3. Set of modelled type C1 C/Q plots with varying peakson the fallinglimb. Again, any alterationin component
Q o and constantQ SE and Q so. Percentageson plot indicate
dischargetimingswhichdoesnot changethis sequencewill not
proportionof peak dischargegeneratedby Qo. QsE and Q so
are the same as in Figure 1. affectthe shapecharacteristics of modelledloops.However,if
the sequenceis altered, hysteresisforms may changesignifi-
cantly. In particular, a reversal of peaks for Q SE and Q so
would changethe rotational directionof all loops.This would
can often alsobe distinguishedusingC/Q plots. Most impor- invalidateinterpretation,althoughas discussedearlier sucha
tantly, a simple 2CM cannot generate the convexhysteresis scenariois expectedto be fairly unusual. A more realistic
types C1 and A1; this would require that CT tends towards possibility,observedby Bazemoreet al. [1994], is that ground-
valuesboth higher and lower than the pre-eventvalue. If any water maybe laggedbehindsoilwater. Given that groundwater
one solute exhibitsconvexhysteresis,this therefore suggests cannotby itself causeCT to deviatefrom pre-episodevalues,
that a 3CM is necessary.Similarly, a 2CM cannot generate the impact of this changemay be limited. However, a large
concaveloops in combinationsother than thosegiven above. delayed groundwaterinput is likely to distort C/Q relation-
If, for example, type C2 and C3 loops occur in the same ships,and the methodsdescribedshouldnot be appliedto a
episodefor two different solutes,a 2CM can againbe rejected. systemin which this situationis thoughtlikely. In practice,it
may be possibleto identifysucha systemwhere inferredcom-
2.4. Stability of Modelled C/Q Loops ponentrankingsare clearlyunrealistic,althoughobviouslythis
So far, C/Q plots have been generatedfor a single three- requiressomeprior knowledge.
componenthydrograph,using a singleset of componentcon-
centrations. It is therefore useful to consider the extent to 2.5. Effects of Temporally Varying Component
Concentrations
which plots retain a similar form if conditionsalter. Three
aspectswhich may vary are componentconcentrations,com- An inherent assumptionof the model used, and of mixing
ponent dischargemagnitudes,and componentdischargetim- modelsin general, is that componentconcentrationsremain
ings. constant.The violationof this assumptionwill only affect C/Q
The rankingof componentconcentrationshas alreadybeen formswhere componentrankingschangeduringthe episode.
identified as a critical determinantof hysteresisform. Beyond One situationin whichthismay occuriswhere solublematerial
this, however,absolutecomponentconcentrationshave no ef- hasaccumulatedprior to the event,for instancebecauseof dry
fect on the shapecharacteristics definedabove.The only situ- depositionor biologicprocesses. Flushingis likely to generate
ations where different forms will arise are special casesin high event water concentrationsat the start of the episode,
which two componentshave the same concentrations.If the followedby exhaustion[Wallingand Webb,1986].Significantly,
C SE= C so, plotswill approachthe curvilinearform shownin in a 2CM thiscantransforma typeC3 loopinto a typeC1 loop,
Figure 3a. If Co is equal to one of the other components,the which could otherwisebe produced only by a 3CM, if event

(a) CSE= Cso > CG (b) Cso > CSE= CG

.a 70

õ•o

I '1 o 40 I I
0 20 40 60 0 20 40 6O
Discharge(arbitraryunits) Discharge(arbitraryunits)

Figure 4. Modelled C/Q loops for which two componentshave equal concentrations.All component
dischargesasin Figure 1. (a) Cso = 150,CSE= 150,andCo = 50. (b) Cso = 150,CSE-- 50, and Co = 50.
 EVANS AND DAVIES: CONCENTRATION DISCHARGE HYSTERESIS 133

water concentrationsinitially exceedpre-event levels. Given Table 2. C/Q HysteresisClassifications,

Summer/Fall
the possibilityof flushing,then, a C1 loop cannotbe taken as Events, Adirondack Streams
definite evidencefor a 3CM. It shouldbe noted in this respect, Clock- Anti- No Dominant
however,that type A1 hysteresiscannot be generatedby a Variable Events wise clockwise Hysteresis Type(s)
2CM, evenwith flushing(as thiswouldimplyincreasingrather
than decreasingeventwater concentrations). The observation ANC 25 24 0 1 C1 (12), C3 (8)
Na+ 25 22 0 3 C3 (19)
of a type A1 loop for one or more solutesis therefore an
K+ 25 20 2 3 C1 (18)
importantconfirmationthat a 3CM is in operation. SO•- 25 0 25 0 A1 (18)
In a 3CM the impactof flushingwill dependon the type of
loop normallyobserved,havingmostsignificance where CSE
would otherwisebe low. In general, hysteresisform will be
transformed(with increasinglevelsof flushing)accordingto section,analysishas carried out for four chemicalvariables:
the sequences A1 ---->
A2 ---->
C2 or A3 ---->
C3 ---->
C1. Although ANC, Na+, K+, andSO42-.
problematicfor interpretation,flushingshouldusuallybe iden-
tifiable among a set of C/Q plots. Within a single episode, 3. Results
risinglimb CT peaksfor a flushedsolutewill precedethosefor
3.1. Adirondack Streams
normaltypeC1 or C2 solutes.Additionally,asflushingis most
likely after extendeddry periodsor autumnleaf fall, the oc- Spatial differencesin resultsbetweenAdirondack streams
currenceof typeC1 or C2 loopsfor a givensoluteonlyat these are minor, and they are consideredas a group.However,there
timesmay suggestflushing.A solutewhichexhibitsthesehys- are significantseasonalvariationsin behavior.C/Q plots for
teresisforms throughoutthe year is probablynot affectedby snowmeltepisodestend to be stronglyopen-ended,probably
this process. becauseof dilution of groundwaterby infiltrating meltwater.
Of the other components in the 3CM, Cso is thoughtlikely These episodesare therefore unsuitablefor analysis.Spring
to be fairly stable,as equilibriumreactionssuchas cationand episodeswere generallyundersampled,and only six couldbe
anion exchangeminimize temporalvariations.It is possible analyzed.Theseshowedrelativelysubduedchemicalvariation,
that Ca maydecreaseduringepisodes,asweatheringreactions consistentwith the suggestionof Hooperet al. [1990] that soil
maybe too slowto offsetdilutionby infiltratingeventwater.In water may dominaterunoff duringthis period becauseof wet
this situationpostepisodeCT will not return to pre-episode conditionsand low-intensityprecipitation.
values,givinga readilyidentifiable"open-ended"loop. Summer/fall events were better sampled, and C/Q plots
conformed well to theoretical models. These were therefore
2.6. Analysis of Stream Data consideredin detail. A total of 25 episodesmet minimum
The methodsdevelopedfor C/Q analysiswere applied to sample criteria (five to sevenper stream), and these were
ERP data from four streamsin the SouthwesternHighlands classifiedas shownin Table 2. Where more than 75% (an
regionof theAdirondacks: BaldMountainBrook,BuckCreek, arbitrarythreshold)of eventsfit a givencategory,the number
Fly Pond Outlet, and SeventhLake Inlet. The first- and sec- of is highlighted.Figure 5 showsC/Q plots for an intense,
ond-orderstreamsare locatedclosetogetherand havebroadly 1-hour June thunderstormat Fly Pond Outlet.
similar characteristics.All are underlain by Precambriangra- ANC exhibitsclockwisehysteresisin 24 out of 25 episodes.
nitic gneisses and metasediments andcoveredby sandyglacial All fully classifiableloops are typesC1 or C3, both of which
till. Soils are Spodosols,and all basinsare forestedwith a suggestthat soil water is the most acidicrunoff source.The
hardwood/conifermixture. Wetlands in low-relief valley areas highestANC componentappearsto varybetweengroundwater
are believedto generateSOF. and surfaceevent water. The C1/C3 split occursmainly on an
Of five monitoredstreamsin the Pennsylvaniaregion, Linn interstreambasis(sixout of eighttype C3 loopsoccurat Buck
Run and Benner Run had sufficientmonitored episodesfor Creek) and is not thoughtto be linkedto flushing.
analysis.The second-order, forestedbasinshavenot been gla- Twenty-twoout of 25 episodes showclockwise Na+ hyster-
ciated and are underlainby sandstoneand some shale.Soils esis,of which all 19 classifiableloopsare type C3. This implies
are mainly acidic Hapludults and Dystrochrepts.Basinsare a highlyconsistentcomponentrankingof Ca > C sE > C so.
larger than thosein the Adirondacks,and loadingsof atmo- K + hysteresis is alsoclockwisein 20 episodes, but a predomi-
sphericpollutantsare higherin this region.BennerRun con- nantlytype C1 classification indicatesa componentrankingof
tains wetland areas close to the stream, while Linn Run has a CsE > Ca > Cso. Hysteresistends to be less pronounced
higherrelief and doesnot containwetlands.Linn Run is more duringfall, and two Novemberepisodesactuallyexhibit anti-
acidic.Further detailsof all watershedsare givenby Wigington clockwisehysteresis. It is believedthat soil water K + is de-
et al. [1996]. pletedduringsummerbut increases to a levelcomparableto or
For analysis,episodeswere required to be single-peaked, greater than surfaceeventwater in fall.
with at leasttwo samplescollectedon eachlimb of the hydro- SO42-hysteresis isremarkably consistent,with anticlockwise
graph,and one at or closeto peak discharge.This wasconsid- loopsin all 25 summer/fall episodes.
Eighteenare classifiableas
ered to be the minimum from which rotational direction could typeA1. From the earlierdiscussion the observationof thishys-
be determined.Identifyingcurvatureoften requiredadditional teresistype stronglysupportsthe useof a 3CM to interpretob-
samples,but the exactnumbervariedaccordingto the typeof servations.
The impliedcomponentrankingis Cso > Ca > CsE.
loop and to the times at which sampleswere collected.The
mostcommonlimitationwasinsufficientsamplingof the short- 3.2. Pennsylvania Streams
duration rising limb. Full classification
was undertakenonly Eight episodeswere suitablefor analysisat BennerRun, and
where curvaturecouldbe characterizedand where a loop cor- 13 at Linn Run. These were fairly well distributedover the
respondedto one of the modelled forms. In the following year, and strongseasonalvariationsin resultswere not evident
134 EVANS AND DAVIES: CONCENTRATION DISCHARGE HYSTERESIS

(a) ANC (b) SO4

400 150

300
200
100
• •-125
=.E.100
O
• 75

0 .... 50 ,.
2 4 6 8 0 2 4 6

Discharge (cfs) Discharge (cfs)

(c) Na (d) K
110 25

100 20
•- 15
80
70 =.E.
10
60 5
50- - - - ß : 0 , , ! , , i, , , , !

0 2 4 6 8 0 2 4 6

Discharge (cfs) Discharge (cfs)

Figure 5. C/Q plots for June event, Fly Pond Outlet, Adirondacks.

(partlybecausesnowmelteventsdid not occur).Classifications common to streamsin both regions,despite differencesin

for eachstreamare shownin Tables3 and 4. C/Q plots for a geology,soils,topography,and depositionloadings.It is pre-
fall event at Benner Run are shownin Figure 6. dictedthat in the Adirondacks(duringsummer/fall),surface
For Benner Run, resultsshowa strikingsimilarityto those eventwater hascharacteristically highK +, highto moderate
for the Adirondacks.All eventswith ANC data showtype C1 ANC, andlowSO42-. Groundwater hasa fairlysimilarANC
hysteresis,givinga rankingof CSE > Co > Cso; soilwater is andhighNa+. SoilwaterhashighSO42-andlow ANC and
againthe mostacidicflow source.Where observed,Na+ hys- Na+. A comparison can be madebetweenthesepredictions
teresis is also clockwise,with a C1 or C3 classification.K + and previous measurementsmade at similar locations.The
exhibitsclockwisehysteresisin six episodes,classifiedas type Adirondackstudiesconsideredhere are thoseby Mollitor and
C1 in five. The C SE> Co > C so rankingis the sameas that Raynal[1982],David andDriscoll[1984],Cronan[1985],Shep-
for theAdirondacks. SO42-hysteresis is anticlockwise
in seven ard et al. [1990]and Fosteret al. [1992].All studiesmonitored
out of eight events,all classifiableas typesA2 or A1. Either mineral soil water, and some give values for lakewater or
suggests thatsoilwaterhasthe highestSO42-. streamwaterwhichare usedto representgroundwater.Surface
Hysteresisat Linn Run is lessmarked than at Benner Run eventwater was consideredpotentiallyto be either unaltered
for most solutes.ANC exhibitsC1 or C3 type hysteresisis six throughfallor to undergomodificationat the surfaceduring
episodes,and no clearpatternsemergefor Na+, whichis low overlandflow. Unfortunately,none of the studieslisted sam-
and fairly invariantat this stream.Type C1 K + hysteresis is pled overlandflow, and it is doubtfulthat hillslopeorganic
observedin four episodes,all of whichtook place in the June- horizonleachaterepresentsa suitableproxygiventhat SOF is
November period. For the remainder of the year, concentra- likely to occurin wetland areas.
tionsremainat a low level.SO42-is moreconsistent, with 10 If it is assumedthat throughfallrepresentssurfaceevent
out of 13 episodesshowinganticlockwisehysteresis.SIX of water,SO42- predictionsarein excellent agreement withpre-
thesecanbe classed astypeA1, suggesting thatCso > Co > CsE. viousmeasurements. All studiessupportthe predictedcompo-
nent rankingof Cso > Co > CSE.Similarly,measurements of
K+ indicateasexpected
thatCSE> Co > Cso.K + isleached
4. Discussion
from organic material but tends to be adsorbedin mineral
Results generallyindicate consistentpatterns of C/Q hys- horizons[Likenset al., 1994].Althoughthroughfallenrichment
teresisfor the solutesanalyzed.A numberof thesepatternsare wouldbe sufficientto explainobservedhysteresis,it is consid-

Table 3. C/Q HysteresisClassifications,Full Year, Benner Table 4. C/Q HysteresisClassifications,

Full Year, Linn
Run Run

Clock- Anti- No Dominant Clock- Anti- No Dominant

Variable Events wise clockwise Hysteresis Type(s) Variable Events wise clockwise Hysteresis Type(s)

ANC 7 7 0 0 Cl (7) ANC 13 6 1 6 C1 (3), C3 (3)

Na+ 7 5 0 2 C1 (2), C3 (2) Na + 13 2 4 7 none
K+ 7 6 0 1 C1 (5) K+ 13 4 0 9 C1 (4)
SO4
2- 8 0 7 1 A2 (5), A1 (2) SO42- 13 1 10 2 A1 (6)
 EVANS AND DAVIES: CONCENTRATION DISCHARGE HYSTERESIS 135

(a) ANC (b) SO4

40 160

30 .--. 140

20 ß 120
v

10 '•' 100
o
0 , ! , o• 80
-10 60 ,
5 10 0 5

Discharge(cfs) Discharge(cfs)

(c) Na (d) K
5O 25

2O
.--. 40

v
= 30

z 20

lO ! i 0 ! !
5 10 0 5 10

Discharge(cfs) Discharge(cfs)

Figure 6. C/Q plots for Septemberevent,Benner Run, Pennsylvania.

ered likely that further K + is releasedfrom the watershed hysteresisis observedduring this period, but concentrations
surface.Where overlandflow hasbeen sampled,albeit at quite are uniformly low for the remainder of the year.
differentbasinsin Amazoniaand Queensland,it appearsthat Previousmeasurementsin Pennsylvaniahavebeen givenfor
K + increases
significantly
on contactwith the surface[Elsen- PeavineHill by DeWalleet al. [1988b]and for Fish Run (a
beeret al., 1995a, b]. ANC was not measuredin any of the tributaryof Linn Run) by Swistock et al. [1989].Measurements
previousstudies,but an indicationcan be gainedfrom values have also been made of shallowsoil water, throughfall, and
givenfor H +. As expected, groundwater is relativelyalkaline, baseflowby the firstauthorduringfall 1995at BennerRun (C.
and soilwater is acidic.However,the consistentlyacidicnature Evanset al., manuscriptin preparation,1997).Again, overland
of throughfallappearsto be at oddswith the high ANC pre- flow was not sampled.All three studies,like thosefor the
dictedfor surfaceeventwater from C/Q analyses.It is thought, Adirondacks, supportpredictions of highSO42-in soilwater
however, that this discrepancycan be explained by surface andhighK + in throughfall. ANC (on the basisof H + values)
interactions,particularlywithinwetlands.Hill [1993]hasshown is highestin groundwaterbut lower than expectedin through-
thatconcentrations
of Ca2+,Mg2+,andNa+ in throughfall
can fall relativeto soil water. Na+ is alsolowestin throughfall,
increaseby 35-50% within a minute of contactingwetland whichis inconsistentwith the C SE> C so rankingindicatedby
substrates.This would explainhigher than expectedANC in clockwisehysteresisat Benner Run. This againsuggests that at
surface event water. Na + results are also consistent with this BennerRun at least,surfaceeventwater is modifiedby contact
hypothesis;previousstudiesshowhigh levelsin groundwater, with the watershed surface.
but throughfall concentrationsare lower than those in soil
water. Again, therefore,somesurfaceinteractionis necessary
5. Conclusions
to explainobservedhysteresis (althoughnot presentedhere,
thesamefindings areobtained for Ca2+ andMg2+). It has been demonstratedthat C/Q hysteresistakes on one
Before comparingPennsylvania resultsto previousstudies,it of a rangeof characteristic
formsdependingon the flow system
is usefulto examinedifferences betweenthe two streams,par- in operationand takeson the rankingof soluteconcentrations
ticularlywith regardto Na+ andK +. At BennerRun, Na+ is in different components.While, as emphasizfidby Christo-
thoughtto derivefrom a groundwaterbrine source.As a result, phersenand Hooper [1992], absolutecomponentconcentra-
behavioris similar to that in the Adirondacks,where Na + is tions cannot be determined from stream data alone, the meth-
mainlyweathering-derived[Munsonet al., 1990;Evans et al., odspresentedhere make it possibleto predict relative values
1996].At Linn Run there appearto be neither major weath- basedon simplecriteria.
eringor brinesources, andNa+ is consistently low. Contrasts C/Q hysteresisobservedfor the Adirondack and Pennsylva-
in K+ hysteresis maybe explained by hydrologic differences. nia ERP streamshas been interpreted in terms of a 3CM of
At Benner Run, wetland areasgeneratesignificantSOF, and groundwater,soil water, and surfaceevent water. The hydro-
interactionwith surficialmaterialsproduceshigh surfaceevent logic model used is thought to be realistic in terms of flow
waterK + throughout theyear.At Linn Run,withoutwetlands, generationtheoriesand is consistentwith most previous3CM
surfaceeventwater inputsare thoughtto be limitedto direct hydrograph separations. In general, predicted component
channel interception [DeWalle et al., 1988a; Swistocket al., rankingsfor a range of solutesagreewell with measurements
1989].Thiswill retaina throughfallcomposition, with K + en- obtainedduringother studies.This would seemto supportthe
richmentconfinedto the growingseason.As a result,type C1 assumptions of the modelused,in that an invalidmodelwould
136 EVANS AND DAVIES: CONCENTRATION DISCHARGE HYSTERESIS

not have givenrealisticresults.Those discrepancies which do the chemicalcompositionof four streamsin the Adirondack Moun-
arise can be explainedby base cation releasefrom wetlands tains, New York, J. Hydrol., 185, 297-316, 1996.
Foster, N. W., M. J. Mitchell, I. K. Morrison, and J.P. Shepard,
during saturationoverland flow. It is also apparent that the
Cyclingof acidandbasecationsin deciduous standsof Huntington
exact nature of "surfaceevent" water may differ betweenba- Forest,NewYork, andTurkeyLakes,Ontario,Can.J. For.Res.,22,
sins;in the AdirondackstreamsandBennerRun, it is thought 167-174, 1992.
to consistmainly of saturationoverlandflow, whereasat Linn Fulcar, G. E., Determination of the componentsof stormflow in
Run it may be confinedlargelyto direct channelinterception. streamson an urbanizedand forestedbasinusingoxygen-18,M.S.
It is thoughtthat the methodspresentedhere may be appli- Thesis,98 pp., Schoolof ForestResources,Pennsylvania StateUrii-
versity,UniversityPark, 1990.
cable to a wider range of basins,althoughclearlyit is essential Gillham, R. W., The capillaryfringe and its effect on water table
that a particular basin shouldconform to the assumptionsof response,J. Hydrol.,67, 307-324, 1984.
the hydrologicmodel used.The approachshouldprimarilybe Hendrickson, G. E., andR. A. Kreiger,Geochemistryof naturalwaters
of use for those studies,such as the ERP, where component of the Blue Grassregion•Kentucky,U.S. Geol. Surv.WaterSupply
compositions
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Hewlett, J. D., and W. L. Nutter, The varyingsourcearea of stream-
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in which componentshave been identified and sampled,in water wetland,WaterResour.Res.,29, 2663-2673,1993.
Hinton,M. J., S. L. Schiff,andM. C. English,Examining
the contri-
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fundedby the U.S. EnvironmentalProtectionAgency,However,the Jenkins,A., R. C. Ferrier, R. Harriman, and Y. O. Ogunkoya,A case
manuscripthas not been subjectedto the EPA's internal review and studyin catchmenthydrochemistry: Conflictinginterpretationsfrom
doesnot necessarilyreflect the viewsof the Agency;no officialen- hydrologicaland chemical observations,Hydrol. Processes, 8, 335-
dorsementshouldbe inferred,We hppreciatecommentsmadeon the 349, 1994.
manuscript
by DaveDeWalleandhisassistance,
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othersat Pennsylvania
StateUniversity,duringfieldwork.We alsowish istry before, during and after snowmelt,paper presentedat Inter-
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G.I.U.B.-Hydro-Biogeochemistry,
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