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VOL. 22, NO. 13, PAGES 1749-1758, DECEMBER


A Direct Distribution Model for Regional Aquatic Acidification

Departmentsof Civil En•7ineerin•7 En•7ineerin•7 Public Policy, Carne•7ie-MellonUniversity, Pittsbur•7h, and and Pennsylvania
A model is developed to predict the regional distribution of lake acidification and its effect on fish survival. The model predicts the effect of changesin acid deposition rates on the mean and variance of the regional distribution of lake alkalinity using empirical weathering models with variable weathering factors. The regional distribution of lake alkalinity is representedby a three-parameter lognormal distribution. The regional pH distribution is derived using an explicit pH-alkalinity relationship. The predicted pH distribution is combined with a fish presence-absence relationship to predict the fraction of lakes in a region able to support fish. The model is illustrated with a set of 1014 lakes in the Adirondack Park region of New York State. Significant needs for future research for regional aggregation of aquatic
acidification models are identified.



meanandvariance theregional of alkalinity distribution. The
primary advantage of this is that the alkalinities of an entire population of lakes are representedby a single set of equations, instead of applying the model to each individual lake. The approach is similar to that of Joneset al. [1984], who use Monte Carlo methods to synthesizeregional distributions of alkalinity and fish presence,but in this case,regional chemistry is represented by analytical continuous distribution functions.

The processes affecting acidification of aquatic systemsare complex. Important factors include the hydrology and geochemistry of the watershed,soil processes such as weathering, ion exchange,and adsorption, plant uptake, and chemical and biological reactions in the receiving lake or stream. Damage to fisheries likewise involves complex mechanisms, including the impairment of reproduction, damage to young fish and resulting reductions in recruitment, direct kills during pHdepression/metals-elevation events, and losses realized through the food chain. Dynamic, mechanisticmodels have been developedto simulate acidification processes with varying degreesof detail and sophistication [Chen et al., 1979, 1982; Christophersenand Wright, 1981; Schreiber, 1982; Galloway et al., 1983; and Cosby et al., 1985]. These models are important for detailed study and evaluation of individual watersheds,and they provide a framework for advancing the state of knowledge of the fundamental mechanisms acidification.For regional assessof ment, however, predictions are required for many lakes; as many as a few hundred to a few thousand in some areas. Execution of a detailed dynamic model for each lake is a formidable task, as is the collection of the physical and chemical data necessary calibrate and verify the model for each of to the watersheds. Alternative approachesto regional assessment are clearly required. To meet the need for regional prediction, empirical equilibrium models have been developed that utilize steady state chemical weathering and ionic electroneutrality [Henriksen, 1979; Thompson, 1982; Kramer and Tessier, 1982; Wright, 1983, 1984; Wright and Henriksen, 1983; $chnoor et al., 1984, 1986; $chnoor and $tumm, 1984]. These models calculate a steadystate lake alkalinity correspondingto a given acid deposition rate. While the equilibrium models are easier to apply than their dynamic counterparts, several difficulties remain when they are usedfor regional assessment. One such difficulty is that weathering rates are known to vary significantly in different watersheds.The approach presentedin this paper addresses this explicitly by using random variablesto representchemicalweatheringand lake alkalinity in a region. The acidificationmodel is applied directly to the
Copyright 1986 by the American GeophysicalUnion.
Paper number 6W4378. 0043-1397/86/006W-4378505.00

Alkalinity is the fundamental state variable in the equilibrium modeling approach. As used here, it is the acid neutralization capacity of water and can be either positiveor negative.A single value of alkalinity (e.g., an annual average) is assigned to each lake. To predict the average value of lake alkalinity, equilibrium models utilize simplified representationsof weathering processes.Thompson[1982] assumesa constant rate of basecation generationin the watershed.Wright and Henriksen [1983] assume a constant fraction of the acid load is neutralized by the release of base cations. Schnoor and Stumm [1984] assumea nonlinear relationshipbetweenthe alkalinity generation rate and the level of acid deposition, based on observed mechanisms of mineral hydrolysis. Alkalinity moment relationshipsare derived for the Henriksen-Wright model and the Schnoor trickle-down model in the following

Existing equilibrium acidification models are designed to predict the alkalinity of individual lakes. To apply these models to the mean and variance of the regional alkalinity distribution, a number of assumptionsand transformations are required. The following sectionsdescribe the HenriksenWright and Schnoor acidification models and the assumptions and transformations needed to apply them to regional prediction.

2.1. Henriksen-Wright Acidi. fication Model The Henriksen-Wright model relates the equilibrium alkalinity of a lake to the acid deposition rate, annual rainfall, flow-through ratio, and chemical weathering in the watershed. A fraction F of the incoming acid load is assumedto be neutralized by chemical weathering, cation exchange, or oxidation-reduction processes,resulting in the generation of base cations. The remaining fraction (1 -- F) decreases lake the alkalinity, given by

Alk = Alk o --(1 -- F)D/lOOOPR


lake F P weathering•ation exchange factor. However. rate R runoff flow-throughfractionfor the lake resulting from evapotranspiration The varianceof Alko is determinedby solving(6) for the positive root of aAlao' O'Alko ---[Cc20'F2(p 1)q-O'Alkc2] CcO'FP (8) 2 -1/2 -The mean and the variance of the weathering factor are Equation (1) is simplifiedby defininga depositionconcentration' C .1970]. and fi = kh/lOOOPR. to illusof varianceof each [e.F) (3) lake sulfate and base cation concentrations in the region may also be used to infer values of F [Wright.the SchnoorTrickle-Down model. 1986].only wet deposition conIn is sidered and C is estimated by F is identified for a region.9.while C is assumedconstant.5 [Schnooret al.a)/2 (9) av2 = (b . Parameter Estimation for the Henriksen-Wright Model scaling factor indicating the relative magnitude of neutralizaParameter estimation is based on a set of current alkation processes. Lake to lake variability in alkalinity can again linitiesAlk½ from whichthe moments estimated: are #Atkc and be attributed to differences in each of the input parameters.Benjamin and Cornell. #Atkomean zero-deposition regional alkalinity. Positive correlation is expected between Alko and F. F.2. as is discussed previously.1750 SMALL AND SUTTON: DIRECT DISTRIBUTION MODEL where 2 all O'Alkcß Assuming Alk current or predictedlake alkalinity (#eq/L).g. The result of the nonlinear formulation is that the fraction of the of acid acid load which is neutralized decreases as the amount ar 2 variance the weathering of factor.#A. Schnoor dominant variation in alkalinity across a region. annual precipitation (m/yr).2 2Ca where 2 2 (6) ko rate constant the absence freeacidity in of (#eq m. [1985]).C(! . Alko. Referred to as the tricklebe modifiedby allowingAlk. equal to F. the lakesof the regionare in equilibrium with the currentdepositionCc..#r) (5) where W -. whereAlko = ko/lOOOPR.perhapsin lake to lake variations in each of the inputs and parameters' the range of 0.D/(1000PR) so that (2) estimated based on a geochemicalassessment the region. of consideringsoil and rock characteristics and the relative watershed and lake sizes. kh rate constant for acid hydrolysis. but incorporatesa chemical weathe regional alkalinity are determinedby applyingrelation. moment relationshipsare now derived for an alternative weaof in the lake to lake variabilityin deposition (He) and flow. respectively. Schnoor Trickle-Down Model to variancein Alko and F..In contrast. rrAtko variance thezero-deposition 2 of alkalinity' #r mean weatheringfactor' Based on observed watershed mineralogy. this fraction is assumedto remain constant in the Henriksen-Wright model. #Alko #Alkc Go(1 #r) -'4-- (7) D aciddeposition (#eqm-2 yr-•)..0-0. through fraction (R) is assumed be small relative to the 2.(3) can the kinetics of chemical weathering.(ko q. deposition increases. The mean alka.8. The resulting variance Alk depends The Henriksen-Wright formulation is used in the example in upon the sensitivity the model to eachparameterand the application presentedlater in this paper. and R. asymmetrictriangular. The steady state lake alkalinity in the trickle-down model . P. triangular. Alko.kaOm)/1000Pa (11) and.Hp is calculated the volume as weighted So for example. This constrainsapplicationof the methodologyto geographic regions and $tumm.C(1-.most likely positive.1). and a distribution shapeassumed (e. p correlationcoefficient betweenthe initial alkalinity and the weathering factor.down model. The latter thus accountfor the preSchnoor and coworkers[Schnooret al..Given this. D.if F is assumedto be uniformly distributed averageof hydrogenion in all precipitation eventsover the year. the value of rn is typically estimatedto be about 0. the mean and variance are C = HeIR (4) ttr = a + (b .then the mean and variance follow directly. the currentstudy.a)2/12 (10) where e is the average H hydrogen concentrationpreion of cipitation (#eq/L).3.Aaoarp k -Jr.0533.-. 1984] derive a lake acidification model based on over which depositionis relativelyconstant. While the trate the generality of the modeling approach.). The correlationcoefficientof Alko and F The variability in alkalinity across regionis determined a by is.1-0.The chemical weatheringrate is related to the rate of acid linity is deposition by #A. Information on the distribution of Alk = Alko . term fi is a The 2. 1983].The mean and variance of Henriksen-Wright model. the steady state version is similar to the ables.D/lOOOPR (12) tion increases (Reussin the work by Johnsonet al.uniform. allowingfor correlationbetween initial alkalinity and the the weatheringfactor. rn fractional order constant. 1986. etc.2 yr. 1984. over the range 0. the mean and varianceof F are 0. For a uniform distribution over the range a to b..thering rate W that variesnonlinearlywith acid deposition. alkalinity sensitivity Alk to changes each of the inputsis similar.the mean zero-deposition alkalinity is calculated as Alko zero-deposition alkalinity(#eq/L). and F to be random vari.the alkalinity varianceis O'Al --O'Alko C20'F-Jr.5 and 0.0. as can be expressed as watershedswith a higher initial alkalinity should also respond with greater weatheringand cation exchangeas acid deposiAlk: Alko + fid m-.g. If the range of The value of C may be determinedfrom both dry and wet deposition. shipsfrom Benjamin and Cornell[1970] to (3).theringformulation..

(31) .= la. A result of this assumptionis that the values of coand •p in (24) and (25) remain constant. variance. The relationship is expressed the form in pH = a + b arcsinh (Alk . When such is the case..d)/c or its inverse ttx = 0 + exp (• + (p2/2) ax2 = co(co. Alkalinity moments for projected deposition concentrations are then computed by (5) and (6). The three-parameter lognormal function was selectedbased on its ability to fit observeddistributions and easeof estimationand computation. 5 X(1)X(n)Xø'$2 (26) where X(•) is the minimum.•. Estimation of the mean and varianceof the zero-deposition mate 0: alkalinity is again made using a set of current alkalinities and assumed values tto.(18) and (19) are usedto estimate the corresponding mean and standard deviation of the current Observed distributions of regional alkalinity are generally characterizedby unimodal functions with significant positive skew. three.(X)(X. and better fits are obtained using the method of Stedinqer [1980] to estinonlinear effectsof rn and the use of/• in place of F. Implementation of the direct distribution model with the trickle-down formulation is left for future studies.•tk a. -. and (p are the parameters of the distribution. and pseudomaximum likelihood Although the trickle-down model provides a more general representationof weathering reactionsthan that given by the Henriksen-Wright model. However.5 the ) estimatesfor • and 05: O'Atko = [Dc2mo'o2(p•2 + O'Atkc __ __1) 211/2 Dcr.. REGIONAL ALKALINITY DISTRIBUTION FUNCTION These are not true maximum likelihood estimates. has a probability densityfunction(pdf) givenby Alkalinity is often used as a metric for determining the acidification status of lakes.2.t•p• (16) median of n observations. The values of rn.. and 0•. •. and 7. which would require a more complex model. •. and the equations for the mean and variance of the alkalinity are laA. D. + (13) 0 $t•-. A lognormal random variable X.1) exp (2•) 7x= (co../a. 4. and Weibull distributions. (p2= In (to) (25) These equations are similar to (5) and (6).. 2.andp•' of O'fl la..+•) = exp (• • =• InLcø( 1) FzL] cø _ -. and 4• can be estimated for a current Because (29) and (30) are monotonically increasing.o• 2= 2 q2m O-t•p where (14) 3to mean value of/•' (24) rrt• variance 2 of/•.1)•/2(co 2) + where (18) (19) (20) (29) Alk = d + c sinh (pH -. such f. In areas impacted by acid depositionlower tails often extend into the range 0 to -100 $teq/L. pH may be a more appropriate indicator.½•]2 2 ni=l (X unknown. a.[alk(pH)] = where alk(pH) is computedfrom (30).and the Johnson$u distribution. for certain estimates. and R are thus assumedto be constant for the region. X(n the maximum. In the example presented later.o lairD"'--D/lOOOPR .•u. and four parameter functions. the physically based pH-alkalinity relationship developed by Small and Sutton [1986] can be used to transform a predicted alkalinity distribution to the corresponding pH distribution. = laA. the methodology for implementation of the model in a direct distribution framework is •=1 •ln(X_0) ni=l 0•=1 • [ln .. including the type 1 extreme value alkalinitydistribution. DISTRIBUTION OF PH (Gumbel) distribution' three-parameter lognormal.a)/b (30) co= exp (052) (21) The parameters 0.•. The modified values of 0 and • are computed from (22) and (23). cand These values used are in (7) and (8) to determine the zero-deposition alkalinity moments.4. and skewness coefficient of X are as the determination of fishery status. This preserves basic shapeof the the distribution as it is shifted in responseto changing deposition levels and eliminates the need to predict changesin the skewness coefficient.and Xo.0). which representsalkalinity. as estimates of ko... These distributions are described in detail in the work by Johnson and Kotz [1970]. The estimated skewness coefficient determined from (20) is assumed to remain constant throughout. kh. of and the inverted forms of (18)-(21): FvH(PH) F.o.0)(p(2/l:){-[ln(X-0)-•] = exp I 1/2 . gamma. the CDF of regional pH can be computed directly from the CDF of regional alkalinity: alkalinitydata set usingsample estimates ttx. and m become more readily available. Attempts to fit observedregional alkalinity distributions were made using a variety of two. P. but include the However. since 0 is Given 0. •. (27) (28) the•D½"' D½/lOOOPR o c + (15) 0=X(1) q-X(n) --2Xo. 2(p2 2}(17) where 0..I (22) (23) O'Atk O'Atko O'l•2D q-2Dmo'. p• correlation coefficientbetween the initial alkalinity and/•.•u. the HenriksenWright formulation is used. The mean.SMALL AND SUTTON' DIRECT DISTRIBUTION MODEL 1751 but the primary source of variability is assumedto result from differencesin Alk o and •. this generally leads to poor estimation. 3. while upper tails may extend beyond 1000 tteq/L in areas with a high degree of buffering.

ILLUSTRATIVE EXAMPLE EISa] =fp Si(pH)f•a(pH )dpH (36) H Use of the direct distribution model is now demonstrated Numerical integration is required to evaluate this expression. a•.• c. Estimate 0.. Marcus et al. Si(pH). Data Requirements 2. Prior to demonstrating the use of the direct distribution model. Correlation coefficientp betweenchemicalweathering factor and zero-deposition lake alkalinity. Determine uncertain.. and (32). which may be the major cause of fish Ridge and Brookhaven National Laboratories for the Nationmortality. •. and X is the vector of water quality constituentconcentrations. In addition. the relationship should account for periodic excur. Baker and Harvey. the example minum. and •p from lake alkalinity data using 3. tion.watershed morphology. estimatethe parametersof (36) for various fish species [Baker. Integrate (36) to determine the expected fraction of lakesin the regioncapableof supporting fish species. Hudy et al. 1983. The exampleis intendedprimarily for chemicalmodel by replacingpH with X throughout. 1981.Acid ChemistryInformation Databasecompiledby the Oak sions from the average. 1.. Determineao and a• for the fish viability function. REGIONAL FISH IMPACTS 1. the data used to estimatethe Si(pH) functionmust be basedon A fPa(PH) fAtk[alk(pH)] (32)number of studiesprovide long-termaveragevaluesof pH. ) )2. reflects an estimate based on a time-averaged pH at each lake.). The valueof •pin (25) is assumedto remain constant. The fish viability function may then be expressedas (18)-(21).The lakes lie within the . the curIn rent study we consider only a univariate relationship on the parameter pH.(1 + exp(ao + a•pH)). with a set of 1014lakesin the AdirondackState Park region Equation (36) may be generalized for a multiconstituent of New York State. Calculatepredictedvaluesof • and 0 from (23) and (22). 5. scaleresponse acid deposition. and Yau. data 4. etc. 1985]. alu. c. using where St is the survival probability of speciesi. 1985. 1983. fpa(PH)={•cosh(PHb--a ) 6. and calcium.. Fish viability S•(pH) refers to the probability of speciesi survival in a single lake or stream. 6..estimatedin a preliminarymanner.1. Alkalinity and pH valuefor eachlake in the region.. Calculatepredicted valuesof •lAt and O'Alfrom (5) and k k for brown trout later in this paper. and many of the parameters in the model are cant intraregional covariance of parameters such as pH. Since the factors which influence the magnitude of al Acid PrecipitationAssessment Program and includeresults pH depressions are generally the same as those which influfrom a variety of samplingprograms. Chemical lake data usedin the example are a subsetof the As such. Reckhowet al.and the factorswhich influto The fish viability function used in the following example ence it.1752 SMALL AND SUTTON: DIRECT DISTRIBUTIONMODEL The probability densityfunction for pH can also be derived directly by dAlk ence average pH (soil thickness. opment of the method. 5. ß ([d--O+csinh(PH•a)lck(2•z)•/2)-• (33) The utility and limitations of (29) and (33) are demonstrated in the example presentedlater in this paper. 1985. lake chemistry aluminum) are highly correlated with pH. and manner in which an S•(X) function is estimated from observed interesting insightsare gainedinto the nature of the regional data [Reckhow et al. it is reasonable to use a viability function based on the averagepH. it is useful to summarizethe data requirementsand 2qb 2 6. (30). q-anXn) ! (34) (26)-(28). For a regional prediction the fraction of lakes or streams able to support speciesi is determinedas the expectedvalue of Si: corresponding the predicted to ttA.• (35) As a number of other important chemical factors (such as Finally. A common functional form for presence-absence relationshipsis the logistic regressionmodel [Berkson. Fish species presence-absence as a functionof pH. 6. 1981.. requiring illustrative purposes as the extent to which the data set is a joint probability distribution function for regional chemical representative the overall populationof lakes in the region of concentrations. using (7) and (8) for the o o Henriksen-Wright formulation.. et APPLICATION ß exp{-[ln(d-O+csinh(PHb-a)) operations as follows. this covariance affects the does illustrate the power and flexibility of the method. Estimates of the mean and variance of the chemical 3. weathering factor. given by 5.. 1944.and aAtn. the 7. to implement the predictive model. However. Averagerunoff flow-throughfraction for the region R.1983. 3. Determine fitted valuesof ttAu. and aaU.1986]. other parameters are still (6). quite important and should be consideredin the future devel2. However. The ability of fish to survive dependson a variety of complex interacting factors.Such a function must incorporate the signifi. it is expectedthat and fish populationestimates differentdeposition for levelsare the single parameter function can provide an effectivepredicdeterminedby the followingsteps. 1985]. to = d-• information which can be used Combining (17). b. and d for the pH-alkalinity relationship in (29) using nonlinear regressionmethods describedin the work by Small and Sutton [1986]. Wiener.Haines.c. Current acid deposition rate. As illustrated for the fish viability relationshipdeveloped 1.Baker.2. Determine a.. 4.Reckhow al. Operations Si(X = (1 + exp(ao + a•X• + a2X2 q.

equivalent H•. [1984].4 [Wriqht. representing only sensitive systems.646 Fitted/•Atkc 91 /•eq/L = FittedrrAtkc137/•eq/L = Fitted 7atn.2.216 EstimatedAlkalinity Distribution • I-I Observed 0 = -99. The correlation coefficient be- 7.the mean and standarddeviationof the weathering factor. and averagevaluesranging from 0..S. Comparisons the observed of and fitted cumulativealkalinity distributionsare shown in Figure 2. Fish Presence-Absence Relationship a0 = 16. recentsurveyconductA ed by the U..1. and each lake was assigneda single value for pH and alkalinity. Observedquantiles(open circles)shown for every twentieth lake.75 are reported others[Johnson al.Runoff. [1983. Location of Adirondack State Park Polygon.with a pH meter.2. AssumedModel Inputs Inputs for the direct distributionmodel include the level of acid depositionconcurrentwith the lake chemistryobservation period. . and the correlation coefficient between the zero- depositionalkalinity and the weatheringfactor. Fig. 2. and Weathering togramare shownin Figure'3-. polygonillustrated Figure 1.0. Summaryof Parameter Estimatesfor Direct Distribution Model Applied to 1014 Lakes in Adirondack Parameter tweenchemicalweatheringand zero-deposition lake alkalinity is assumed to be 0. 1985].8. Assumed valuesfor theseparameters summarized the first section are in of Table 1.5 p = 0.teq/'L to [e. 1984]. 3.For for the current study all inferences limited to the set of 1014 are lakes considered.35/•eq/L pH-Alkalinity Relationship -100 0 100 200 300 400 500 Alkalinity (Heq/1) Fig. 1958' Schnoorand Stumm.. 1983' Stensland. 2. 1983]. whichis described detail by in in Gmur et al. with the mode at 0. 1984]. Fitted Alkalinity and pH Distributions Valuesof 0. and qb the currentalkalinity distribution for were estimated for the 1014 Adirondack lakes using (26)-(28) Park and are givenin Table 1.FittedLognormal ComputedZero-Deposition Alkalinity /tatno 143/•eq/L = a = 5. However. 1.45 to 0.53 = • c5 -. as the sampleincludesresultsfrom a number of surveyscollectedfor differentpurposes. Reussin the work by Johnson al.04 •b= 0. Observedand fitted probabilitydensityfunctionof alkalinity for 1014 Adirondack lakes. 1983' Wriqht.22 c . Data utilized in this example include only alkalinity measurements performed using the Gran plot method.g.0 tteq/L { = 5. The data base is not necessarily representativeof the overall population of approximately 2800 lakes in the Adirondack region. B0 W 79 o W 780 W 770 W 760 W 750 W 740 W ?30 W Longitude Fig. the runoff flow-through fraction for lakes in the TABLE 1. region.%96/•eq/L aatno=121/•eq/L b = 0.49 ax = . Precipitation during 1974-1982is estimated be about pH to 4. = 65 /. 7. in most cases. 1983].6 and a standard deviation of 0. and pH measurementstaken.216. Discussion the techniques of usedfor data compilationand quality assurance given in the works by is Hendrey et al.SMALL AND SUTTON' DIRECT DISTRIBUTION MODEL 1753 O• rved d Lognormal Adirondack Polygo New York State •o -100 100 300 500 700 900 Alkalinity (peq/1) . Observed frequencyhistogram shown for alkalinity intervals of 50/•eq/L.Based thislimitby et on ed evidence.5 /•i= 0. Observedand fitted cumulativedistribution function of alkalinity for 1014 Adirondack lakes.3.4343 (= 1/In 10) d = 7. Environmental ProtectionAgency [1985] utilized stratified samplesof regional lake chemistryand should provide improved population estimates future studies.Dana. equal to the median of the reported values. The runoff flow-throughfractionis estimatedto be 0. and the corresponding probabilitydensity functionand his- Estimates Assumed Model Inputsfor Deposition.39 . [1985] suggests et that this value is probably low.01. Values of the chemicalweatheringfactor in sensitive regions have been reported to average about 0.5 [Thornthwaiteet al.6 = aF = 0. resultingin a mean of 0. 1979' Banqay and Riordan.the chemicalweatheringin the Adirondacksis represented a triangular by distribution overthe rangeof 0.5. •. All observationsused were collected during 1974-1982. The fitted alkalinitydistri- Hp = 65/•eq/L R = 0.

To derive the predicted distribution of pH. bution provides a generally good representation. and Chester are plotted in Figure 10. though as expected. Note the clustering of observationsat pH values of 5. c. This is appropriate in a geochemicalsense in that some watershedsare expected to generate little or no alkalinity. ductivity.0 has a nearly linear responseto changesin the precipitation acidity.ø .5 units. Estimated values of a.5. As the acid deposition is reduced as good as for the alkalinity distributions which are directly to zero. Cox. while another larger group is for the most part unaffecacid deposition result in shifts in the regional distributions of ted. Distribution of alkalinity.5-7. along with the relationship fitted using regressiontechniques [Dixon. Data from Muniz et al. Impact of Chan•Tes Deposition in of lakes with a pH that is significantlyimpacted by acid depo7. Following the procedure summarized in As is indicated. Fish Population Response --Derived Distribution øI . i [)/øo • . As can be seen in Figure 10. though the number of lakes with alkalinity near zero is underestimated. In terms of the regional processof acidification.g. Changes in the level of sition. Figure 7b also suggestsa larger Note that the fraction of lakes below pH 5.500 7oo •oo 4 5 6 7 Alkalinity (peq/1) Fig. are quite significant. As is indicated in Figure 8a.. Distribution of pH. the regional alkalinity distributions predicted to acid deposition on the regional alkalinity or pH distribution is result from acid deposition reductions of 50 and 100% were to examine the fraction of lakes below a given alkalinity or determined and are shown in Figure 7. Currently.below 5. pH Observed and fitted pH-alkalinity relationship for 1014 Adirondack lakes. and the corresponding probability density function and histogram are shown in Figure 6. 5. The fitted parameters for pH (35) are given in Table 1. and d are given in Table 1. one way to depict the effect of changesin section 5.:' ':L.0 as a function of the acid deposition rate. and 7.1. Observed and derived cumulative distribution function of pH for 1014 Adirondack lakes. Note that (35) is fitted using a least squares approximation for grouped survival data partitioned according to pH classes. Fig. values for the four parameters of the pH-alkalinity relationship in (29) are required. of reduced acid deposition. 6.4343 (1/ln 10).3. predominant range of about 5.2. 6.-" ' ' Fitted . though considerablescatter is evident at higher alkalinities. Figure 9 shows the fraction of lakes with pH density functions shown in Figure 7b clearly illustrate the in. [1984] and Chester [1983]. The shifted probability pH. and a. c. and the fitted relationship is compared to the observeddata in Figure 4. these lakes are predicted to increase in pH to the fitted. particularly in a predominantly clear water region such as the Adirondacks. 1981].The magnitude of the predicted shift results from the fact that many of the lakes are currently poised near the steeppart of the pH-alkalinity titration curve. the corresponding changesin the derived pH distributions. 4. indicating an apparent tendency to report pH observations rounded to the nearest unit. the pH-alkalinity relationship provides a good representation.'. .':'. Observed derived and probability density function pH of for 1014Adirondack lakes.5. Observed quantiles (open circles) probability of fish viability is significantlycorrelated with conshown for every twentieth lake. 1981]. For example. the parameter b is fixed at 0. As indicated. This is consistent with the observed fraction below served distributions is indicated. It is interesting that the minimum value of alkalinity predicted for a 100% reduction in depositionis relatively closeto zero. Although the shifts of the alkalinity distributions in Figure 7 appear to be is not pH 5.1754 SMALL AND SUTTON' DIRECT DISTRIBUTION MODEL I--I Observed m Derived D•str•but•on ?.this suggests that there is a subgroup 7. I . with a pH The two parameters of the fish viability function are estimated for brown trout using results presented by Muniz et al. 7.Observed frequency histogram shownfor pH intervalsof 0. General agreement between the derived and ob. but these lakes would only become acidic as a result of the input of atmosphericdeposition. the Fig. alkalinity and pH.5. as well as with pH.below 5. shown in Figure 8.A more o involved maximum likelihood procedure is required to estimate the relationship from (ungrouped)presence-absence data 3 4 5 6 7 8 for individual lakes [e. creased mean and decreasedvariance of alkalinity as a result about 25% of the 1014 Adirondack lakes are in this category.3. Comparisons of the derived and observed cumulative pH distributions are shown in Figure 5. 1970]. responsein low-alkalinity lakes where weathering factors are likely to be low.3. shown in Figure 5. about one third of the lakes are currently modeled to be significantly impacted.4. The importance of calcium (a oObserved •o//• 7. Following Small and Sutton [1986]. I I I 1 -100 loo aoo . and d are estimated by nonlinear least squares regression[Dixon.

1981. Although this dependenceis ignored in this analysis. . In particular. . In this paper we present only a widely recognized [e._C_u rt r_en //. 17.•)'s iRt .including The sensitivity analysespresentedin this section consider emissionsand atmospheric transport modules [Rubin et al.3 pH units to the right (a0 = and behavior rSpear and Hornberger.-.. 7.on ".'"..eod: c 'i ø•? 3 4 5 6 7 ----.. •Current •. some sults of the sensitivity analyses are summarized in Figures lakes may not have fish for reasonsother than acid deposition. the major features of model behavior. The values of/9 considered in Figure 14 tion is reduced by 50%. 1978. Analysesof this type are currently being performed for indicates less tolerance to acidification.51)and 0.g. Cosby et al.47).current fraction of lakes able to support fish.8) is relationships which approach a value less than one as pH representative of the current range of estimated weathering increases. The parametersexaminedinclude the mean and variance of This is especiallysignificantfor areas recoveringfrom acidifi.. The fraction of lakes if all watersheds in the region have F. with corresponding the direct distribution model as part of its implementationin lower fractions predicted in Figure 15. Zero Deposition -100 100 300 500 700 900 -100 0 100 300 300 400 500 Alkalinity (peq/1) Fig.and the parameters of the fish viability relationship. of on predominant component of conductivity) to fish viability is 1984' Marnicio et al. holding other parameters conIt is important to remember that the fish viability function stant at their nominal values.3 pH units to left (a0 = 15.6.-• CDF •/"""" . The sensitivity analysis shown in Figure 15 demonstrates 7.4-0..5.0. weathering process. Sensitivity Analysis that modifications in the fish viability function change the A variety of techniques are available to examine the sensi. only simple single-parametervariations." '.0.. Alkalinity (peq/1) Predicted effectof 50 and 100%reduction aciddeposition regionalalkalinitydistribution. The minimum (at = 0) occurs using (36) and are shown in Figure 11. Changesin butt. the maximum currently able to support brown trout is predicted to be about (ar = 0. 8 3 4 5 6 7 8 pH pH Fig.this value being the fraction of lakes expected to factors and is consistent with current understanding of the support a given speciesin the absenceof acidification.. restocked.. 12-15. where fish popultions may not return unlessthey are tween the weathering factor and the zero-depositionalkalinity.cover the range of likely positive values.60% have F = 1.SMALL AND SUTTON' DIRECT DISTRIBUTION MODEL 1755 o.The range of weathering factor standard Predictions of the fraction of lakes able to support brown deviations consideredspan the minimum and maximum possitrout as a function of the acid deposition rate were generated ble values.In addition.44) occursif 40% of the watersheds have F = 0 and 78%. Gardner et at.A shift to the right 1985]. A result of this is that it may be appropriate to use viability The range of mean weathering factors considered(0. as well as the tivity and uncertainty of predictive models [e. PDF • Current 5zOe rPoe. 1985]. and to decreaseto 63% if acid deposi.•..•tsiRt ZerøD/// '50ieodnUCt Per Iøn x '• 0 • • b."• _-----50 Reduct.. Zero Deposition . The repriate for natural versus stocked populations.. model parameters are varied. Brown. .. Cox and Bay..the regional weathering factor.6.. and it can be seen tion is increased by 50%..g. Uncertainty in the o. an integrated assessment model of acid deposition. Finally.. the correlation coefficient becation. shown in Figure 10 representsthe potential to support fish. few examplesof simplesensitivityanalysisto illustrate someof 1982].. 1980. This value is predictedto increaseto 92% if acid deposi.50 PercentReduction . that the model is relatively insensitiveto this parameter.. 1981]. Among the most effective of the parameter ao were produced by shifting the presencethese are methods which incorporate observed system data absencecurve (Figure 10) by 0. Predictedeffect of 50 and 100% reduction of acid depositionon regional pH distribution.el/•.fraction predicted for different levels of deposition.."'". Wright and Snekvik..PDF. Percent • . CDF Current /'• b. 8... we demfuture versionscan incorporate this effect through the use of onstrate how the results in Figure 11 change when individual multiconstituentrelationships.. different viability curvesmay be appro.given that Pr = 0.

I • MLt• I C < •0 uS/cm I -. 1985.g.. DISCUSSION the dynamicsof watershedresponse.librium at the same rate. We model.Considerableprogress has been made in the develtion problem [Rubin et al. Cosby et al. Fraction of lakes with potentially viable brown trout population as function of acid deposition. by their very nature.. 1985]. •"-. examination of the impact of structural uncertainty on model predictions is an important priority for future research. 9. and the presenceof sulfate clusionin an integratedassessment model of the acid deposi. Significant needs for future research have been identified and include application of the methodologyto survey data properly stratified to representthe overall lake population of a region. uS/cm / •'• o [] • Muniz:>20 ChesterK /• . basicstructureof the underlyingmodelsis alsosignificant..weathering reactions. simplifythe physicalprocesses environmental systems. Observed probabilities southern for Norway from Muniz et al. o o . a distributionfunctionother than the lognormal may better fit the regionaldistribution of alkalinity. For example... the selectionof lag factors is largely judgspheric transport models have been replaced by source. Sensitivityof predictedfish impact to changes assumed in value of mean weatheringfactor. Similarly. Hp(•eq/1) Fraction of lakes with pH less than 5. soil depth...In order to accomplisheffectivemodel tion.1984] for low and high conductivity. Hp(peq/1) Fig.if weatheringprocesses properly represented are by the nonlinear equations of the Schnoor trickle-down model. For example. or do some portions move more lem components. Current 2. [1983] and Schnoorand Stumm [1984] discussthe factors which influence 8. then there is no selectionof a regional F distribution for the The current model predicts the steady state status of lake chemistry and biology._____•. though advances in current research should lead to receptortransfermatricescomputedfrom the original models... 10.. the use of more advanced weathering formulations such as the trickle-down model. do all portions of the distribution shift toward equimodelshave beendeveloped and utilizedfor eachof the prob. 11... particularly for linked modelsof the type developed this study. 1..rapidly? For now. and even more so for a regional distribution.F•tted Function 5 6 7 4 25 50 75 100 Lake pH Fig. Other important limitations in the model include the need to consider the dynamics of watershed responseand the need for field validation.1756 SMALL AND SUTTON' DIRECT DISTRIBUTION MODEL L Fig. the extension to multiconstituent chemical distributions. though and Rubin.. An important next step is to consider the dynamics of lake response.. fundamental improvements in this assessment. . 1985].0 as function of acid deposition.5 50 75 100 Precipitation Acidity. 25 50 75 100 Precipitation Hp(peq/1) Acidity.adsorption. 12.4 y' explorethe broad scaleaspects alternativepolicy have explored the use of lag factors to model the temporal of formulations. including the kinetics of The model presentedin this paper was developed for in. the In Henriksen-Wright model that will exactly predict the regional response. 0. though the conceptual difficulties are considerable. and to examine critical scientific uncertainties responseof lake chemistry and biology to changing deposiand researchneeds.and Chester1-1983]. 1984. detailed long-range atmo. Precipitation Acidity. and the fuller evaluation of model uncertainty. or the fish-viability relationship may deviate from the logistic form assumed. Fig.This problem is common to all mathematical modelswhich. Marnicio et al. These issuesare addressed in the remainder of this discussion section... simplified representations of more sophisticated example. in The direct distribution model representsa similar attempt to simplify existingaquatic modelsand has been fully incorporated in the integrated assessment model. Galloway et al..mental.. This assessment links models of the various dynamic prediction remains a challengingtask for an individcomponents of the acid deposition problem into a single ual lake. For linkage. Small opment of dynamic models [e. ••'F: ' . Fish presence-absence relationshipfor brown trout. addition..While judicious selectionof of parametersmay lead to acceptablerepresentations system of responseand estimates of uncertainty.

Y. F. mentation with more advanced weathering formulations. and funds from the Claude Worthington Benedum Foundation. mean and variance of the regional weathering factors. This researchwas supportedin part by a grant from the U. J. 13. REFERENCES 0 25 50 7. (2) impleimportant part of future studies. Schnoor.vides a beginning for addressingthe need for regional aggregation in the modeling of aquatic acidification. Using preliminary estimatesfor weatheringparameters. Inputs requiredby the model includealka.D.. SUMMARY AND CONCLUSIONS extension to multiconstituent chemical distributions.Initial sensitivityanalysesindicate that the magnitude of of individual lakes and watersheds. Baker.o o 25 50 ß Current 75 100 0 25 50 Current . a greater variance of weaadvances. However.. confidencein the model may be are illustrated using an estimated presence-absence based in part on the success the underlying mechanistic ship for brown trout. N. N. However. A number of interestingresultsare portrayed in the illustraThe present model is calibrated using current deposition. 15. and (6) uncertainty analysis inlinity and pH valuesfor eachlake. Fish viability predictions in relationavailability of these data. These include the need for (1) application with regionally stratified survey data. McMichael. Precipitation Acidity. Fig. E. A. and J.. Current Gmur.A full validation of the modeling procedure must await the docu.• 75 100 Precipitation Hp (•eq/1) Acidity.S. this requiresintensivesampling and modeling studies eries.Cornell Univ.thering rates..impacts for individual lakes. Church. Sensitivity of predicted fish impact to changesin assumed value of standard deviation of weathering factor. tion of lakes able to support fish is found by integrating the pH distribution with a fish viability function. The model predicts the proved. ic models. Ph. the acid depositionrate. Marmorek.SMALL AND SUTTON' DIRECT DISTRIBUTION MODEL 1757 ¸ ¸ -o.and greatercorrelationbetweenF and Alko. Kaplan provided data and technical support for the analysisof the Adirondack region. J. (i•eq/1) Itp Fig. Bartuska. D. A number of limitations in the model and needs for contincessfulcomparisonswith more detailed models that operate on a lake by lake basis. Reckhow. Hoogendyk. application of regional equilibrium models should provide usefulinsights the eventualapplicationof regionaldynamfor Acknowledgments. Sensitivityof predictedfish impact to changes assumed in value of correlation coefficient between weathering factor and zerodeposition alkalinity. and such comparisonswill be an ued research are identified. Environmental Protection Agency as part of the National Acid Precipitation AssessmentProgram (NAPAP). (3) 9. C. An explicit func. Rubin. The regional model is thus the regional responseto changesin acid deposition increases dependenton thesedetailedmechanistic studiesfor conceptual with a lower mean weatheringrate. Harvey. (5) comparison with models which compute and fish resources.shiftsin the lake chemistry. Sensitivityof predictedfish impact to changes assumed in relationshipbetweenpH and species presence/absence. NAPAP Proj- . and H. dissertation. R. Aluminum toxicity to fish as related to acid precipitation and Adirondack surfacewater quality. of the regional distribution of lake alkalinity. and E.Prior to the a subgroup of lakes in the region.and fish presence-absence data. Ithaca. and no official endorsement should be inferred. Baker. Useful advice and suggestions were provided by J. Baker. methods are neededfor applying these models to reeffectof changesin acid depositionon the mean and variance gional evaluations in an integrated assessmentframework. Critique of acid lakes and fish population status in the Adirondack region of New York State. K. Fig. it regional alkalinity distribution are predicted for given rehas not been validated for changesin deposition. Confidence in the model can also be built by suc. tive example with lakes in the Adirondack Park region. indicating the potential for viable fishof models. and a While aquatic acidification models continue to be imregional correlation coefficientbetween weathering factors and the zero-deposition alkalinity.The application of the direct distribution approach with emtion relating pH and alkalinity is used to derive pH distri.5 100 Precipitation Up(peq/1) Acidity.The resulting shift in the regional distribution of pH indicatessignificanteffectsfor mentation of shifts in regional distributions resulting from known changes the quantity of acid depsition.The frac. 1981. the corporating structural and parameter uncertaintiesand their impact on linked models. 14.ductions in the level of acid deposition.pirical weathering models and fish viability relationshipsprobutions from the predictedalkalinity distributions. it has not been subjected to NAPAP's required peer and administrative review and therefore does not necessarilyreflect the views of NAPAP. (4) conA model is developedto calculatethe impact of changes in sideration of the dynamic properties of the regional approach acid depositionon the regionaldistributionof lake chemistry to equilibrium.

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