Journal of Hydrology, 26 (1975) 237--244

Elsevier Scientific Publishing Company, Amsterdam -- Printed in The Netherlands

V A R I A T I O N S IN T H E N A T U R A L C H E M I C A L C O N C E N T R A T I O N O F R I V E R W A T E R D U R I N G FLOOD FLOWS, AND THE LAG E F F E C T : SOME F U R T H E R C O M M E N T S

D.E. WALLING and I.D.L. FOSTER

Department of Geography, University of Exeter, Exeter (Great Britain)

(Accepted for publication January 8, 1975)

ABSTRACT Walling, D.E. and Foster, I.D.L., 1975. Variations in the natural chemical concentration of riverwater during flood flows, and the lag effect: some further comments. J. Hydrol., 26: 237--244. Following upon the recent paper by Glover and Johnson (1974), the authors briefly present results from several Devon catchments which demonstrate the complexity of variations in the chemical concentration of river water during flood flows. Certain solute species increase rather than decrease in concentration during storm events and the "chemographs" of those species which exhibit dilution are often complicated by a "flushing effect". Some solutes may exhibit variable response, evidencing increased and decreased concentrations during different events. Even in small catchments, the "chemograph" response can lag behind the stream-flow response and examples of where the trough precedes the stream-flow peak have also been documented. Values of "chemograph" lag between zero and 14.5 h have been found at a gauging station on a Devon river and the variation can be tentatively explained in terms of catchment moisture status. Any attempt to account for the nature and timing of "chemograph" response must consider processes operating over the entire catchment in addition to those in the channel.

INTRODUCTION In a r e c e n t paper, Glover and J o h n s o n ( 1 9 7 4 ) have described m e a s u r e m e n t s t a k e n on t h e river S o u t h T y n e w h i c h d e m o n s t r a t e t h a t variations in the c o n c e n t r a t i o n o f certain dissolved c o n s t i t u e n t s t e n d e d to lag b e h i n d associated changes in discharge and t h a t this lag is increased progressively d o w n s t r e a m . This latter p h e n o m e n o n was ably explained on the basis o f k i n e m a t i c wave t h e o r y s u p p o r t e d b y l a b o r a t o r y experiments. The simple dilution o f base flow b y f l o o d w a t e r and the effects resultant u p o n the differential b e t w e e n f l o o d wave velocity and m e a n w a t e r velocity are, h o w e v e r , o n l y t w o o f the m a n y c o n t r o l s acting t o influence the n a t u r e and t i m i n g o f variations in solute conc e n t r a t i o n in streams. Investigations at present being carried o u t by t h e aut h o r s in several D e v o n c a t c h m e n t s are increasingly d e m o n s t r a t i n g t h e c o m p l e x i t y o f this a s p e c t o f physical h y d r o l o g y . M e a s u r e m e n t s t a k e n on small streams can be particularly useful in a t t e m p t i n g t o u n d e r s t a n d the processes involved.

238 In many rivers individual solute species do not all exhibit a drop in the "chemograph" associated with a rise in discharge. Nitrate and potassium concentrations, in particular, often increase during flood events and in Fig.lB the trend of potassium and magnesium concentrations during two storm events in a small Devon catchment is portrayed. Automatic pump sampling apparatus similar to that described by Walling and Teed (1971) was used to obtain these results. In this case, magnesium concentrations exhibit a classic dilution whilst the "chemograph" for potassium shows a marked increase in concentration. In order to explain this occurence, the several pathways between the input of precipitation and the resultant channel flow must be considered. The various rates of solute pickup, and the resultant concentrations in comparison to those in the preceding base flow will govern the precise behaviour of the "chemograph". Furthermore, detailed study of the "chemographs" of those solute species exhibiting a drop during storm events often indicates that something more than a simple dilution is involved. In many instances, and particularly during autumn months, the decrease in concentration may be preceded by a rise, or an initial drop may be followed by an increase before giving way to a subsequent decrease. This occurence has been termed the "flushing effect" by several authors (e.g., Edwards, 1973; Walling, 1974) and can be accounted for by the flushing of accummulated solutes into the stream by the initial phases of storm runoff. In Fig. 1A the occurrence of this flushing effect is demonstrated for a small Devon catchment, the data again having been collected with an automatic pumping sampler. In this case, the "chemographs" for calcium, sodium, and magnesium associated with the first stream-flow rise exhibit an initial decrease in concentration, followed by an increase and a subsequent drop. During the second stream-flow rise this flushing effect is absent. In Fig. 1C, a continuous record of specific conductance has been used to define the trend of the total dissolved solids "chemograph" for two storm events on a larger Devon river. In both cases a flushing effect is evident. The precise extent of this flushing effect during an individual flood event will influence the timing of the drop in the "chemograph". Again the pathways to the channel taken by the storm-period runoff must be considered and the chemical character of the inflow to the channel should be recognised as being time-variant according to the detailed temporal and spatial pattern of solute pickup. Certain ionic species can demonstrate variable response, exhibiting increased concentrations during certain storm events and decreased concentrations during others. Nitrate levels in particular often demonstrate very complex behaviour of this type and another specific example is provided by fluctuations in potassium concentration in a small stream (Fig. 1). On most occasions, potassium levels in this stream increase markedly during storm hydrographs (Fig. 1B) but, during a series of closely spaced storm events, concentrations associated with the later hydrographs may demonstrate a dilution effect (Fig. 1A). The precise response of the "chemograph" during a storm event will vary from storm to storm according to many controlling factors.

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240

The authors' observations also suggest that those solute species which consistently exhibit a decrease in concentration during a storm event can respond differently as regards relative timing and that even in small catchments the "chemograph" response can lag behind the stream-flow response. Examples of where the "chemograph" trough precedes the stream-flow peak have also been documented. Fig. 2 depicts the "chemographs" of calcium, magnesium and sodium for three individual storm events in another small catchment equipped with automatic pump sampling apparatus. In this catchment, the "chemographs" generally exhibit a well-defined minimum value or trough and the authors prefer to define lag on the basis of the relative timing of the stream-flow peak and the solute trough, as originally conceived by Heidel {1956) for sediment. Inspection of Fig. 2 presented by Glover and Johnson {1974) suggests that there may be little difference in the final estimate of lag between their definition and this one. Comparison of Figs. 2A and 2C indicates that whereas in one event the "chemograph" troughs preceded the stream-flow peak, in the other a lag effect is clearly visible. Lag effects in a small catchment are also demonstrated in Fig. 1A where the calcium, magnesium, and sodium troughs lag behind the stream-flow peaks in both events. Furthermore, close inspection of Fig. 2 indicates that the individual solute parameters tend to respond differently as regards timing. In Fig. 2B, the sodium trough occurs before the water peak, whilst the calcium and magnesium troughs lag behind the stream-flow maximum. Contrasts in the general form of the "chemographs" for individual solute species are also demonstrated in Fig. 2A where calcium levels quickly return to those occurring before the storm event, whereas magnesium and sodium concentrations are restored more slowly.

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242

More generalised information on temporal variations in solute levels is also being collected from larger rivers in Devon by continuous recording of specific conductance, a direct reflection of the total dissolved solids concentration in a stream. Specific conductance recording apparatus has been operated at the South-West Water Authority stream-flow gauging station on the river Creedy at Cowley near Exeter since April 1973. The catchment area above this point is 262 km 2. Inspection of the records of river stage and specific conductance for 32 clearly defined single-peaked storm hydrographs indicates that the troughs of the conductivity traces tend to lag after the stream-flow peaks and that the extent of this lag varies from as much as 14.5 down to zero hours where the trough and peak coincide. Two events with lag times of 10.0 and 0.5 respectively are illustrated in Fig. 3A,B. It would seem difficult to explain a range in lag times of this magnitude coupled with the occasional occurence of zero lag times solely in terms of channel routing. An attempt has been made to distinguish factors which could account for the variation in the magnitude of the lag associated with individual flood events. The available data exhibited a general tendency for shorther lags to be associated with the highest stream-flow rises (Fig. 3C and Table I). This is in agreement with the findings of Glover and Johnson (1974). However, in addition to the channel routing controls associated with flood-peak magnitude, consideration can be given to hydrological conditions within the entire watershed. In this context it could be suggested that " c h e m o g r a p h " lags are inversely related to antecedent catchment wetness and storm magnitude. Significant statistical relationships (Table I) have been established between "chemograph" lag and two indices of antecedent moisture condition, namely, flow level preceding the storm hydrograph (Fig. 3D) and soil-moisture deficit (Fig. 3E). Both these relationships demonstrate that maximum "chemograph" lags are associated with dry antecedent conditions and inspection of the data indicates a corresponding seasonal trend in lag magnitude with maximum values occurring in summer and minimum values in winter. A simple harmonic curve has been fitted to the annual distribution of lag values (Fig. 3F) and a significant relationship exists between lag magnitude and the associated seasonal or cosine index for the day (d) on which the event occurred (Table I). A stepwise

TABLE I C o r r e l a t i o n b e t w e e n " c h e m o g r a p h " lag ~ and other h y d r o l o g i c a l variables Variable h y d r o g r a p h rise I preceding flow level ~ soil-moisture deficit season index (cos 2n I ~ Correlation coefficient 2 - - 0.80 - - 0.79 0.71 --0.72

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i Variables t r a n s f o r m e d t o log10. : All c o r r e l a t i o n coefficients significant > 99% level.

243

T A B L E II Stepwise multiple regression equation relating "chemograph" variables "chemograph" lag to the hydrological

lag = 10.364 -- 3.636X 1 -- 1.083X 2 -- 2.965X 3 R = 0.90 w h e r e : X I = l o g h y d r o g r a p h rise ( m 3 s e c -1 ) - l X2 = s e a s o n i n d e x ( c o s 2 ~ r I d~ - 3 1) X~ = l o g p r e c e d i n g f l o w level ( m 3 s e c -~ ) All v a r i a b l e s a n d r e g r e s s i o n c o e f f i c i e n t s s i g n i f i c a n t > 9 5 . 0 % level

multiple regression routine has been employed to develop a multivariate relationship between "chemograph" lag and the four variables described in Table I and the resultant equation in which three variables are significant is presented in Table II. The value of this relationship for precise inferential purposes is restricted because of the obvious interdependence within the independent variables. Nevertheless, it indicates that "chemograph" lags can be predicted to a reasonable degree of accuracy from measures of antecedent moisture condition, magnitude of the hydrograph rise and season. Furthermore, lag time remains inversely related to all three variables. Data from the river Creedy indicates that "chemograph" lag varies markedly according to antecedent moisture status. This tendency is also shown when the stream-flow and specific conductance records for a closely spaced sequence of storm events are examined, in that lag times progressively decrease through the series of hydrographs. A tentative conceptual explanation of this occurrence can be sought in the processes interposed between rainfall input and channel flow and their control by moisture conditions. During conditions of low soil-moisture status, the dry ground surface and upper horizons of the soil will contain accumulations of readily soluble material. Storm runoff will flush this material into the streams and any soil water shunted to the stream by throughflow mechanisms (e.g., Hewlett and Hibbert, 1967) will, by virtue of long residence times, be highly charged with solutes. Furthermore, rapid expansion of areas contributing to storm runoff (e.g., Carson and Sutton, 1971) will introduce fresh solute sources as the storm event proceeds. The solute content of the storm runoff will reach a minimum towards the end of the event when the supply of readily available solutes has been exhausted or reduced and before the increase in solute levels associated with the longer residence time of runoff feeding the recession limb of the hydrograph occurs. The trough of the "chemograph" may therefore lag appreciably after the stream-flow peak. Under conditions of high soil-moisture status, the supply of readily soluble material is likely to have been depleted by previous storm events and the contributing area will be approaching its maximum extent. Solute concentrations in stream flow will fall rapidly at the onset of the storm event, in response to the dilute nature of the storm runoff, and the trough of the "chemograph" will coincide with, or occur very shortly after, the stream-

244

flow peak which itself represents maximum surface runoff rates and in many cases the cessation of storm rainfall. Variations in the natural chemical concentration of channel flow during flood events in both small and large catchments can exhibit marked complexity. The variety of solute response during individual storm events evidenced by these and other catchments under investigation by the authors suggest that a full understanding of the "chemograph" recorded in a river channel will only be achieved if the processes interposed between storm rainfall and channel input and occuring over the entire drainage basin are considered. The effects of channel routing are only one of many controls on the detailed form of the "chemograph".
ACKNOWLEDGEMENTS

The authors are grateful to the Natural Environment Research Council for providing a Research Grant (D.E.W.) in support of work at Exeter, and a Research Studentship (I.D.L.F.) and to the South-West Water Authority for provision of stream-flow records and cooperation with the programme of water quality monitoring.

REFERENCES Carson, M.A. and Sutton, E.A., 1971. The hydrologic response of the Eaton River Basin, Quebec. Can. J. Earth Sci., 8: 102--115. Edwards, A.M.C., 1973. The variation of dissolved constituents with discharge in some Norfolk rivers. J. Hydrol., 18: 219--242. Glover, B.J. and Johnson, P., 1974. Variations in the natural chemical concentration of river water during flood flows, and the lag effect. J. Hydrol., 22: 303--316. Heidel, S.G., 1956. The progressive lag of sediment concentration with flood waves. Trans. Am. Geophyso Union, 37: 56--66. Hewlett, J.D. and Hibbert, A.R., 1967. Factors affecting the response of small watersheds to precipitation in humid areas. In: W.E. Sopper and H.W. Lull (Editors), International Symposium on Forest Hydrology. Pergamon, Oxford, pp. 725--736. Walling, D.E., 1974. Suspended sediment and solute yields from a small catchment prior to urbanization. In: K.J. Gregory and D.E. Walling (Editors), Fluvial Processes in Instrumented Watersheds. Inst. Brit. Geogr. Spec. Publ., 6: 169--192. Walling, D.E. and Teed, A., 1971. A simple pumping sampler for research into suspended sediment transport in small catchments. J. Hydrol., 1 3 : 3 2 5 - - 3 3 7