Ecological Modelling 136 (2001) 81 93 www.elsevier.

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Distribution of particulate and reactive mercury in surface waters of Swedish forest lakes an empirically based predictive model
Martin Lindstrom *
Department of Earth Sciences, Uppsala Uni6ersity, Villa6agen 16, S-752 36 Uppsala, Sweden Received 2 December 1999; received in revised form 31 March 2000; accepted 25 August 2000

Abstract The partition coefcient (Kd) expresses the ratio between particulate bound and dissolved metals. In lake dynamic modelling, it is used to distribute the total load between the dissolved and particulate routes of lake transport. An empirically based model for prediction and evaluation of a modied partition coefcient for mercury (Hg) in lake water has been developed using eld data from 25 Swedish lakes. As a substitute for dissolved Hg determined by ltration, this study uses the easy reducible (or reactive) proportion of Hg in water samples and the modied partition coefcient is here denoted K *. The model relates K * for Hg to the best correlating of several lake specic d d environmental variables, resulting in an r 2-value of 0.69. K * was found to decrease with increasing suspended d particulate matter (SPM) concentration, iron concentration (Fe) and ratio of lake to drainage area (a/ADA). Interpretations of the model parameters were discussed in light of the clusters of statistically and functionally related variables they represent. The negative correlation between K * and SPM is possibly due to the particle concentration d effect, which seems to be valid also for the denition used here for the partition coefcient. For Kd the particle concentration effect is often explained by an exponential relationship between colloids and SPM which results in relatively more colloid bound metals at low SPM concentrations. The fraction of colloid bound metals is counted with the dissolved fraction which decreases the Kd. Inuences of spurious correlations on the relationship between K * and d SPM have been assessed and found to contribute to the statistical correlation. The negative correlation with iron can also be accounted for by Hg association with small particles (iron/manganese oxides and hydroxides, possibly in association with humic matter). The inuence of the morphometric factor a/ADA is probably due to differences in K * with different Hg transport paths (direct deposition on the lake surface is believed to decrease K *). The model was d d tested using stability tests, which indicated that other related variables could replace the given model parameters. The model parameter interpretations, in terms of clusters of related variables would, however, have been similar. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Lakes; Mercury; Partition coefcient; Predictive model; Critical tests

* Tel.: +46-18-4717158; fax: + 46-18-4712737. E-mail address: martin.lindstrom@natgeog.uu.se (M. Lindstrom). 0304-3801/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 3 0 4 - 3 8 0 0 ( 0 0 ) 0 0 3 8 2 - 3

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1. Introduction and aim Thousands of Swedish lakes have sh with mercury (Hg) concentrations above levels considered safe for human consumption (Lindqvist et al., 1984). In lakes with no point sources, atmospheric deposition from remote sources is probably the main transport path (Lindqvist et al., 1991; Fitzgerald et al., 1997). Hg deposited on the lake drainage area is generally xed to soil organic components and leaches only slowly (Lindqvist et al., 1984). Due to the high atmospheric deposition, the pool of Hg is still building up in catchment soils and the problem of high Hg-levels in sh has been predicted (see, e.g. Hakanson, 1996a; Schluter and Gath, 1997) to last for a long time, on the order of centuries. The main transport routes to lakes include transport from the catchment area and direct deposition on the lake surface. The relative importance of these uxes varies among lakes, but they are generally of approximately the same order of magnitude for remote Swedish lakes (Meili, 1991). Hg biomagnies in food chains (Meili, 1991; Mason et al., 1995), and humans might become exposed via consumption of sh (Clarkson, 1990; Fitzgerald and Clarkson, 1991; Clarkson, 1993). Particulate and dissolved fractions of Hg in lakes have different transport routes. Only particulate Hg is by denition subjected to sedimentation (Hakanson and och Jansson, 1983) and, hence, to a higher degree affects benthic organisms. Dissolved Hg, on the other hand, inuences pelagic uxes and planktonic biota. In order to build general mass-balance models for Hg in lakes, it is essential to develop practically useful sub-models for the various processes determining the distribution of Hg within the lake. A predictive model should preferably require only readily available driving variables, such as basic water chemical variables and/or map parameters describing lake morphometry. The partition (or distribution) coefcient is generally dened as the ratio of particulate to dissolved Hg. In this work, the easy reducible (or reactive) Hg concentration will be used instead of the dissolved concentration and the corresponding partition coefcient will be denoted K *. The aim of this article is to develop d

and test a predictive model for K * for Hg which d includes: (1) to study the factors that regulate the variation in K * for Hg among lakes; (2) rank the d factors inuencing this K *-value; and (3) develop d a predictive model for K * for Hg. These issues d have not, to the best of the authors knowledge, been addressed before. Such a model would lead to increased possibilities to simulate Hg behaviour in lakes, and improve the knowledge about the factors determining the distribution between the particulate and reactive phases of Hg.

2. Material and methods For estimation and evaluation of partition coefcients several methods are available. The dissolved fraction may refer to concentrations in true solution (e.g. Tessier et al., 1989, 1993), which includes free metal ions and dissolved organic and inorganic complexes. In many contexts, however, the dissolved concentration is equated with the lterable fraction. In addition to the truly dissolved fraction, this fraction also includes colloidal bound metals that will pass a lter of a certain pore size. Filtration may sound simple but Horowitz et al. (1996) reported methodological problems with this method. Different results were obtained depending on lter manufacturer, water volume and amount of suspended sediment in the sample. Different types of lters and pore sizes are also used, e.g. 0.2 mm (Bloom and Efer, 1990, as referred to in Lindqvist et al., 1991), 0.45 mm (e.g. Seritti et al., 1980; Ahmed et al., 1987; Watras et al., 1995) and 0.8 mm (Mason et al., 1993). For determination of the partition coefcient one pore size is sometimes used to dene the dissolved Hg and another pore size for the suspended particulate matter (SPM), e.g. 0.45 and 0.40 mm respectively (Watras et al., 1995), 0.7 and 0.4 mm (Babiarz et al., 1998). Other methods than ltration may also be used. For example, Boyle and Birks (1999) estimated partition coefcients from atmospheric deposition and sediment concentrations. In this work, a chemical fractionation based on differences in chemical reactivity has been used. The easy reducible (or reactive) part of Hg has been analysed

M. Lindstrom / Ecological Modelling 136 (2001) 8193

83

and used as a substitute for the dissolved fraction to calculate a modied distribution coefcient. Previously published Hg data from an intensive study of 25 forest lakes from south to central Sweden (Hakanson, 1986a,b; Meili et al., 1991; Hakanson and Peters, 1995; Hakanson, 1999), together with a recently developed SPM model (Lindstrom et al., 1999) will be used to develop and evaluate a model for the prediction of K * for d Hg. All selected lakes are situated far from populated areas. They do not have any known point or non-point sources of Hg in the catchment areas. Sampling and analytical methods have been described elsewhere (Iverfeldt and Lindqvist, 1986; Iverfeldt, 1988; Brosset and Iverfeldt, 1989; Meili et al., 1991) and will only be briey mentioned here. Surface water (0.5 m) samples were collected six times during the ice-free period of 1986 in all these lakes. The samples were handled and analysed according to an ultra-clean protocol to avoid contamination (see Lindqvist et al., 1991; Meili et al., 1991). Cleaned glass bottles were used and after sampling they were immediately sent to the laboratory where they were acidied by addition of HCl. The easy reducible Hg is dened as the concentration of purgeable Hg after treatment with SnCl2 in acidied samples, while the total Hg concentration is obtained after treatment with SnCl2 after strong oxidation with BrCl. Volatilised Hg was determined by direct current helium plasma atomic emission spectrometry after preconcentration by double amalgamation (Iverfeldt and Lindqvist, 1986). The quality of the data and reproducibility was tested, and the resulting concentrations have an analytical precision (coefcient of variation) of 9 2% to 5%. Total variation, measured as reproducibility of the whole procedure including (within lake) natural variation and all steps from sampling to analysis, was tested by repeated parallel sampling in different parts of a lake and found to be in the order of 9 20% (Meili et al., 1991). With SPM concentrations estimated by the model of Lindstrom et al. (1999), the modied distribution coefcient K * (l kg 1) is dened d (analogous to Kd) as: K* = Cs/Cw, d (1)

where Cs (mg Hg kg SPM 1) is the measured non-reactive Hg (total minus reactive concentration) (mg Hg l 1) divided by the predicted SPM concentration (kg SPM l 1), and Cw is the reactive Hg-concentration (mg Hg l 1). Since the aim is to derive a model for the among-lake variability in K * lake mean values d will be used in the analysis as the target y-variable. Not only lake water chemical variables will be used as environmental x-variables, but also lake morphometric (i.e. lake size and form) parameters since they have been shown to be important in other lake models (e.g. Hakanson and Peters, 1995). A summary of data and abbreviations used in this work is given in Table 1. There are a number of regression techniques available. Since the focus is on lake ecosystem modelling, the choice of statistical method is, however, generally subordinate to the availability of reliable empirical data. Mean values are here used in a stepwise multiple regression (e.g. Draper and Smith, 1981), correlating K * to the set of lake d specic variables given in Table 1 according to procedures recommended by Hakanson and Pe ters (1995). This method yields statistical correlations which may reveal causal relations, and mechanistical/causal interpretations of the results will be discussed. To get a stable model, the model parameters should show a minimum of interdependence and preferably represent different clusters of related processes. To get an independent residual distribution, the model parameters have been transformed according to Hakanson and Lindstrom (1997). Almost all variables are logarithmically transformed, and a constant factor (0.01) is added to alkalinity values, to avoid the undened logarithm of zero (see Hakanson and Peters, 1995).

3. Results and discussion The distribution of log(K *)-values is shown in d Fig. 1. The mean value is 6.6, the range is from 5.8 to 6.9. This could be compared with results from other investigations. Based on ltration (pore sizes: 0.45 and 0.40 mm for dissolved Hg and SPM, respectively) a mean log(Kd) of 5.25

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Table 1 Summary of data used in this work, n= 25 lakes Variable Mercury (mean 6alues) Total Hg concentration Reactive Hg concentration Distribution coefcient 106 Morphometry Lake surface area Area of drainage area Volume Maximum depth Mean depth Volume development ( = 3Dm/Dmax) Dynamic ratio ( =
(area)/Dm) Mean annual water discharge Theoretical turnover time Water chemistry (mean 6alues) pH Alkalinity Hardness Conductivity Total phosphorous concentration Colour Iron concentration Suspended particulate mattera Abbreviation Unit Mean S.D. Min Max

HgT HgR K* d a ADA V Dmax Dm Vd DR Q T pH alk CaMg cond TP col Fe SPM

ng l1 ng l1 lkg1 km2 km2 km3 m m m3 s1 yr meq l1 meq l1 ms m1 mg l1 mg Pt l1 mg l1 mg l1

5.0 1.4 4.2 0.32 11.94 0.0015 11.7 4.1 1.22 0.18 0.12 0.68 6.0 0.08 0.27 4.3 12.9 95 583 0.77

1.8 0.4 2.0 0.29 12.13 0.0019 7.3 2.2 0.38 0.13 0.12 0.81 0.5 0.09 0.14 2.5 7.0 50 398 0.55

1.9 0.6 0.7 0.04 0.36 0.0002 2.4 1.3 0.73 0.04 0.01 0.02 4.8 0.00 0.12 2.0 6.6 14 63 0.32

9.4 2.3 8.1 1.44 44.16 0.0073 25.2 8.7 2.10 0.56 0.45 3.77 6.6 0.37 0.64 10.8 34.7 258 2051 2.69

a Predicted from the model (based on 26 European lakes with r 2 =0.87) given by Lindstrom et al. (1999): log(SPM)= 1.985+1.148log(TP)+0.137pH + 0.286log(DR).

was obtained for 23 Wisconsin seepage lakes (range 4.26.0; Watras et al., 1995), and 4.9 for seven Wisconsin rivers (range 2.8 5.5; Babiarz et al., 1998), with lter pore sizes of 0.7 and 0.4 mm. The K *-values of these Swedish lakes thus seem d to be high in relation to Kd-values obtained at other sites, which may be due to different methods. The study lakes have, however, low concentrations of SPM (a mean of 0.77 mg l 1, compared to 1.8 and 9.7 mg l 1, respectively of the above cited works) which is a factor shown to control Kd-values (see below). A correlation matrix, showing a rst screening of relations among the given variables is given in Table 2. This table helps to identify clusters of functionally and statistically related variables in the data set. The highest internal correlation for SPM is with the total phosphorous concentration (TP), r = 0.86. This may be considered a cluster representing bioproduction (see, e.g. Dillon and Rigler, 1974;

Schindler, 1977; Wetzel, 1983; Peters, 1986). There are also signicant but weaker correlations with conductivity and water hardness (CaMg). Fe

Fig. 1. Frequency distribution showing the range of mean K *-values, n = 25 lakes. d

M. Lindstrom / Ecological Modelling 136 (2001) 8193 Table 2 Correlation matrix, giving the linear correlation coefcients (r) between the variables, see Table 1, n = 25 lakes log(K *) d log(K *) d pH log(cond) log(CaMg) log(alk+0.01) log(Fe) log(col) log(TP) log(SPM) Vd log(DR) log(a/ADA) log(Q) log(ADA) log(Dmax) log(area) log(V) log(T) log(SPM) 1 0.34 0.60** 0.02 0.09 0.17 0.53** 0.33 0.03 0.08 * PB0.05. ** PB0.01. *** PB0.001. 1 0.08 0.58** 0.47* 0.09 0.47* 0.25 0.72*** 0.77*** 0.35 0.45* 0.17 0.03 0.00 0.41* 0.24 0.01 0.00 Vd pH log(cond) log(CaMg) log(alk+0.01) log(Fe) log(col) log(TP)

85

1 0.34 0.60** 0.92*** 0.48* 0.66*** 0.28 0.10 0.06 0.15 0.23 0.12 0.10 0.03 0.15 0.11 0.28 log(DR)

1 0.91*** 0.31 0.00 0.27 0.51** 0.76*** 0.41* 0.60** 0.10 0.03 0.09 0.48* 0.30 0.00 0.03 log(a/ADA)

1 0.62*** 0.09 0.36 0.38 0.68*** 0.26 0.49* 0.05 0.04 0.10 0.35 0.25 0.01 0.02 log(Q)

1 0.39 0.56** 0.14 0.14 0.08 0.01 0.01 0.02 0.03 0.07 0.03 0.03 0.06 log(ADA)

1 0.88*** 0.57** 0.33 0.16 0.07 0.17 0.00 0.03 0.21 0.17 0.24 0.26 log(Dmax)

1 0.45* 0.15 0.04 0.14 0.25 0.08 0.11 0.08 0.15 0.18 0.28 log(a)

1 0.86*** 0.24 0.21 0.10 0.08 0.13 0.32 0.08 0.09 0.16 log(V)

1 0.41* 1 0.04 0.11 0.04 0.15 0.02 0.23 0.79*** 0.69*** 0.08 0.57** 0.36 0.06 0.31 0.08

1 0.83*** 0.83*** 0.04 0.07 0.08 0.84***

1 0.98*** 0.18 0.58** 0.57** 0.53**

1 0.09 0.61** 0.54** 0.55**

1 0.11 0.60** 0.37

1 0.84*** 0.20

1 0.35

correlates signicantly with water colour, and weaker with TP, indicating a cluster representing small suspended particles such as organic colloids and iron oxides. Coloured substances mainly consist of dissolved or colloidal humic and uvic acids, which are known to be associated with iron oxyhydroxides (Hakanson and och Jansson, 1983; Nurnberg and Dillon, 1993). A morphometric size cluster is formed by the well-known (see Hakanson and Peters, 1995) high correlations among Q, a/ADA, ADA and T. Further, a second morphometric cluster exists for the variables Vd, DR and Dmax. Finally, pH and alkalinity form a well-known cluster. It

should, however, be noted that the internal correlations are complex and related to many different physical, chemical and biological lake processes. The regression model is given in Table 3, and the ranges of the model parameters are shown in Table 1. SPM, Fe and a/ADA are included as model parameters. They represent different clusters and the model gives an r 2-value of 0.69. It is evident from the correlation matrix that the relations revealed by the regression model cannot be explained by only the included variables. The clusters that these variables belong to, have to be considered in the following interpretations.

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Table 3 The regression model for K * for Hg in lake water. For abbreviations see Table 1 d Step 1 2 3 r2 0.60 0.65 0.69 F\ 33 3 2 Variable log(SPM) log(Fe) log(a/ADA) Model log(K *)= 6.4200.803log(SPM) d log(K *)= 6.9520.719log(SPM)0.193log(Fe) d log(K *)= 6.9020.702log(SPM)0.225log(Fe)0.100log(a/ADA) d

The rst and most important variable to statistically explain the variability in mean K *-values d among lakes is SPM (r 2 = 0.60), see Fig. 2. Partition coefcients based on ltration have often been found to relate to SPM, called the particle concentration effect (see, e.g. OConnor and Connelly, 1980; Honeyman and Santschi, 1988; Santschi and Honeyman, 1991; Benoit, 1995; Benoit and Rozan, 1999). One plausible explanation given for this phenomena is that colloid bound metals are measured with the lter-passing fraction (being mistaken for dissolved metals). The relationship between colloid and SPM concentrations is probably not linear, but exponential. For example, the relationship colloid = k(SPM)0.7 is suggested by Benoit et al. (1994). This means that Kd-values should decrease with increasing SPM. For Hg, Babiarz et al. (1998) found decreasing Kd-values with increasing SPM concentrations. The present investigation indicates that the particle concentration effect is not only probable for lter based partition coefcients but also for these K *-values based on chemical d reactivity. In addition to these arguments, is should also be noted that part of the observed relation between Kd (and K *) and SPM might be d an effect of spurious correlations, which may arise when a ratio is correlated to one of the arguments of the ratio (see, e.g. Kenney, 1982), see discussion below. The iron concentration (Fe) enters as the second step with a negative correlation with K *. Due d to the close internal correlation between Fe and water colour (see Table 2) these two variables belong to the same cluster (possibly also including dissolved organic carbon (DOC), which unfortunately has not been measured, Nurnberg and Dillon, 1993; Hakanson and Peters, 1995). In these drainage lakes, colour mainly consists of

humic substances of allochthonous origin and their importance for the Hg distribution within the lake has been recognised before (Nilsson and Hakanson, 1992; Hakanson and Peters, 1995). Humic substances are mainly colloidal and Hg sorbed to such particles would not be retained by a lter to a high degree. Watras et al. (1995) found decreased Kd-values with increased DOC. For Kd, the observed correlation would thus have been interpreted, as a tendency of Hg to associate with small particles which would result in decreased Kd-values with increased iron concentrations. For the present K *, however, the d relationship is more unclear. The negative correlation between K * and the d morphometric variable a/ADA may be understood if the atmospherically deposited Hg on the lake surface would be mostly in the reactive phase. Hg in precipitation has, however, been reported to be mostly particulate or colloidal bound (Lindqvist et al., 1991). This unexpected pattern is discussed also by Meili et al. (1991), and was suggested to be explained by either (1) a signicant amount of dry deposition with another

Fig. 2. Hg partition coefcient (K *) as a function of suspended d particulate matter concentration (SPM).

M. Lindstrom / Ecological Modelling 136 (2001) 8193

87

Fig. 3. Plot of logarithms of observed versus predicted K *-vald ues.

speciation than the wet deposition or; (2) transformations in the lake water of inert Hg to more reactive/dissolved species or; (3) aerosolic associated atmospheric particulate Hg which would settle out rather quick from the lake surface water leaving the more dissolved (reactive) species in the water. The review of Giusti et al. (1993) suggests that the second mechanism might be most plausible. They concluded that atmospherically derived trace metals generally are particulate bound, but that appreciable fractions may dissolve quickly after deposition (the data for Hg is, however, scarce). It should also be noted that atmospheric metals of anthropogenic origin generally are enriched on small particles (B 1 mm). Variables not found to inuence the partition coefcient may also be worth noting. Kd-values based on truly dissolved metals are known to vary with water pH (Tessier et al., 1989, 1993; Hakanson and Peters, 1995). For other Kd-values this relationship is not always found (Benoit 1995; Boyle and Birks, 1999). In these Swedish lakes, pH did not show any signicant correlation with K * (r = 0.08). The range of pH values was, d however, limited, from 4.8 to 6.6. The 34 Newfoundland lakes investigated by French et al. (1999) had a pH range of 4.86 7.72, and no correlation between pH and sediment Hg levels was found. The morphometric parameters Vd and DR showed weak negative correlations with the partition coefcient (r = 0.35 and 0.45, re-

spectively). In predictive modelling these parameters are often used as indicators of sediment resuspension. Weyhenmeyer et al. (1997) found that the sediment focusing (the gradual redistribution of sediment from shallow to deeper areas via repeated sedimentation-resuspension cycles) correlated with DR, and the SPM model by Lindstrom et al. (1999) included DR as an indicator of resuspended sediment. Studies of resuspended sediment partitioning are scarce. Laboratory experiments of resuspension of anoxic sediments in oxic waters indicate that several metals (Hg was not investigated) are released during resuspension (e.g. Petersen et al., 1997; Simpson et al., 1998). More relevant for these lakes, Slotton and Reuter (1995) found no increase in lterable concentrations (which suggest increased Kd-values) in experimental resuspensions (not Hg). The duration of the change was, as well as of the resuspension event, short. In Fig. 3, a plot of the logarithms of predicted K *-values versus measured values show a rather d even t around the regression line. Considering the estimated within-lake variability of K *-values d (about 20%) and the relatively small range of these lakes, there is still room for further modelling improvements.

4. Model stability tests For predictive models it is important to evaluate the model stability. Therefore, a model stability test has been done (according to procedures presented by Hakanson and Peters, 1995). From the original data set of 25 lakes 10 are rst randomly excluded, and the best model calibrated using the remaining lakes. In Table 4 this is repeated 15 times which allows a comparison of model parameters and coefcients with those of the original model. SPM enters in 13 of the tests and is the most stable model parameter. The slope coefcient varies between 1.10 and 0.40 with a mean of 0.75, which is close to that of the original model, 0.70 ( 0.80 in the rst step). It could be noted that for other metals, slope coefcients in the range of 0.9 to 0.5 are generally found (Honeyman and Santschi, 1988; Benoit et

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Table 4 Stability test of the model. For each of the 15 tests, ten lakes have been randomly excluded, thus n= 15. The rst row shows the original coefcients of the original model parameters. Other parameters than the original enter in some of the tests Model parameters and coefcients log(SPM) 0.21 0.23 0.23 0.23 0.23 0.12 0.08 0.20 0.34 0.21 0.43 0.49 0.25 0.13 0.44 0.10 0.32 0.41 0.49 0.34 0.20 35 0.27 0.17 0.10 42 0.23 0.23 0.23 0.27 0.44 0.32 0.26 0.23 20 1.13 0.08 0.09 0.09 0.43 0.00 0.43 0.31 0.43 0.99 0.91 0.80 1.10 0.75 0.40 29 0.31 0.09 0.57 0.86 0.62 0.86 0.50 0.40 0.66 0.52 1.13 0.70 1.10 0.94 0.10 log(Fe) log(a/ADA) log(alk+0.01) log(cond) log(a) log(TP) log(ADA) log(CaMg) log(alk+0.01)

No.

r2

F\

M. Lindstrom / Ecological Modelling 136 (2001) 8193

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

0.69 0.90 0.66 0.80 0.54 0.81 0.37 0.79 0.80 0.72 0.84 0.73 0.34 0.59 0.82 0.86

2 7 2 6 2 2 7 3 10 2 15 6 7 2 6 12

Min Mean Max CV (%)

0.34 0.70 0.90 25

2 5.9 15 68

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89

al., 1994; Benoit, 1995). TP (which is closely related to SPM, r = 0.86, P B 0.001) replaces SPM as a model parameter in test number 3. Fe and a/ADA enter only ve times each, and are less stable as model parameters. In some tests they are substituted by related variables, e.g. in test numbers 5 and 7, ADA replaces a/ADA. The model r 2-value (0.69) is at an average level of the test runs and the F (2) is low. If lakes were excluded not randomly, but according to a given system, the model could be tested in other ways. Table 5 shows a series of tests where the most extreme lakes from different aspects have been excluded (the few lakes with highest/lowest K *, SPM, Fe, a/ADA, TP, pH, d DR and T). SPM enters each model except in numbers 8 and 12, where it is replaced by the related variable TP. In these two tests DR also enters, representing the morphometric cluster. The original model parameters Fe and a/ADA enter in 7 and 5 models, respectively and no systematic effect of excluding extreme lakes can be noted. The variability of parameters is similar for the two tests (Tables 4 and 5), and no other variable would be considered a better model parameter than the original. To summarise the stability tests, one can note that if the model was derived from different sets of lakes it might include other variables. This underlines the importance of performing these kinds of stability tests and to discuss the model in the light of related cluster variables.

from approximately the same statistical distribution as the original data, i.e. a logarithmic transformation of the random data have the same mean value and standard deviation as the data in Table 1. The random number generator of an ordinary PC is used to generate three concentrations, to calculate K *-values from: (1) reactive d Hg; (2) non-reactive Hg; and (3) SPM. To compare with the original model, a matrix of 25 cases (lakes) is randomly generated. Due to the relatively small number of cases (n = 25), r 2-values of the regression of random log(K *) versus rand dom log(SPM) are very variable. For 100 test data sets, the mean r 2-value is 0.32 and the range is from 0.040.72; 2 (i.e. 2%) of the tests yielded r 2-values higher than that of the original model (0.60)! To evaluate the stability of the original regression, one lake at a time is omitted and the r 2value of the regression, using the remaining 24 lakes calculated. This is done 25 times (one for each lake) and the distribution of derived r 2-values is shown in Fig. 4(A), the mean value is 0.59. In Fig. 4(B) the distribution of r 2-values of 100 random regressions using 24 lakes is also shown. The mean value of these is 0.32. To summarise, spurious correlations do seem to offer a possible explanation for a part of the observed correlation between K * and SPM. The mean random r 2-value d is, however, considerably lower than the observed, and part of the relationship could be attributed to the causal explanations discussed above.

5. Test for spurious correlations When a ratio (such as the K *-value as dened d in Eq. (1) or the general Kd-value) is used in a regression versus one of the arguments (SPM), spurious correlation might, by mathematical inevitability, obscure the causal relationships (see, e.g. Kenney, 1982; Jackson et al., 1990; Krambeck, 1995; Berges, 1997). A test is therefore performed to evaluate the probability of spurious correlations. Inuences of spurious correlation on the derived regression model are here tested with a random parameter test. To simulate the real situation, random concentrations are generated

6. Implications for dynamic mercury modelling Reactive Hg has been suggested as a measure of labile inorganic Hg (Mason and Fitzgerald, 1990) and that this is the Hg fraction subjected to methylation. This would perhaps make it possible to use the present model in Hg methylation modelling. It would also be interesting to explore the possibilities to use the reactive Hg, and this model, as a basis for predictions of the distribution of Hg between the particulate and the dissolved fractions. There are several general dynamic models designed for evaluating the fate of Hg in lakes (e.g.

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Table 5 Structured stability test. The most extreme lakes from different aspects are excluded to systematically test the model stability to outliers r2 F\ log(SPM) 0.21 0.30 0.18 0.31 0.16 0.23 0.32 0.32 0.15 0.42 0.24 0.11 0.98 0.35 0.33 0.15 0.17 0.42 0.29 0.17 28 0.17 0.13 0.11 22 0.13 0.20 0.30 43 0.31 0.15 0.16 0.17 7 0.98 0.94 0.90 0.22 0.21 0.19 0.33 0.23 0.23 0.69 0.70 0.90 0.80 0.90 0.65 0.31 24 0.22 0.13 0.12 0.10 log(Fe) log(a/ADA) pH log(CaMg) log(alk+0.01) log(TP) Model parameters and coefcients log(DR) log(a) log(Dmax)

No.

Excluded lakes

0.70 0.31 0.64 0.48 0.81 0.57 0.70 0.71 0.17 0.17 0.11 0.46 0.65 0.68

M. Lindstrom / Ecological Modelling 136 (2001) 8193

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 0.36 0.63 0.79 20 2 3 8 49

3 4 4 4 4 4 3 3 4 3 2 3 3 3 3 3

highest K * d lowest K * d highest SPM lowest SPM highest Fe lowest Fe highest a/ADA lowest a/ADA highest TP lowest TP highest pH lowest pH highest DR lowest DR longest T shortest T

0.69 0.74 0.36 0.36 0.66 0.67 0.69 0.71 0.62 0.49 0.72 0.67 0.59 0.65 0.79 0.68 0.64

2 2 2 2 3 5 2 5 2 3 8 2 4 5 3 3 3

0.90

0.19

Min Mean Max CV (%)

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Henry et al., 1995a,b; Mackay et al., 1995; Hakanson, 1996b; Diamond, 1999) as well as numerous lake specic mass balance models (e.g. Leonard et al., 1995; Vandal et al., 1995). In these models, the partition coefcient of Hg is considered constant. For example, Mackay et al. (1995) used a constant generic value of Kd in a dynamic model to evaluate the effects of different temperatures on the behaviour of Hg in lakes; based on literature data Diamond (1999) used a constant value of 105 (l kg 1); Hakanson (1996b) assumed a constant fraction of 10% Hg in solution (and 90% particulate bound). With a predictive model for Kd, a more careful estimate of Kd could be made, and Kd could be varied with environmental conditions. The effects on Hg uxes of environmental changes such as, acidication or eutrophication could then be simulated. The model derived in this work should be useful from several aspects of dynamic lake modelling, including:

Prediction of lake characteristic K *-values. d The distribution of Hg may be linked to other lake variables. For example total phosphorous concentration and pH, since SPM depends on these variables (e.g. Lindstrom et al., 1999). This would make it possible to dynamically model the inuence of eutrophication and acidication on the Hg fate in lakes. Characteristic variability in mean K * for these d lakes may be estimated with the model. Since characteristic variabilities of the included variables (SPM, a, ADA and Fe) have been studied and assessed elsewhere (Hakanson, 1999), it is possible to calculate also for K *-Hg. d

7. Conclusions It is possible to predict lake water K * for Hg d (based on the use of easy reducible Hg as the dissolved fraction) from lake water chemistry and morphometry. The model shows negative correlation between K * and SPM, Fe and a/ADA. Possid ble causal explanations for these relations have been discussed. The correlation with SPM is suggested to depend on the particle concentration effect. The concentration of colloids is probably exponentially related to SPM. Colloid bound Hg is mistaken for dissolved/reactive which could explain the shown decrease of K * with increased d SPM. Tests showed, however, that part of the statistical relationship between K * and SPM d might be explained by spurious correlations due to the mathematical formulation of K * as a ratio. d The correlation with Fe is probably explained by a similar mechanism, small colloid Fe-humic complexes, which sorb Hg, might be accounted for as dissolved/reactive. Finally, the relation with a/ ADA could be interpreted as differences in the partitioning of Hg from the two main transport paths to these lakes. Hg deposited directly on the lake surface could have a more reactive behaviour than Hg transported from the drainage area. The model was tested using stability tests, which showed that the model parameters could vary depending on the lake data set. Another set of lakes would result in other model parameters, but the interpretation (based on the recognition of

Fig. 4. Histogram showing the distribution of regression r 2values between log(K *) and log(SPM), for (A) a stability test d of the regression model (Table 3); and (B) 100 K * and SPM d values randomly generated from the same distribution as the one used in (A). 24 lakes/random cases are used in both (A) and (B).

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M. Lindstrom / Ecological Modelling 136 (2001) 8193 Dillon, P.J., Rigler, F.H., 1974. The phosphorus-chlorophyll relationship in lakes. Limnol. Oceanogr. 19, 767 773. Draper, N.R., Smith, H., 1981. Applied Regression Analysis, second ed. Wiley, New York, p. 699. Fitzgerald, W.F., Clarkson, T.W., 1991. Mercury and monomethylmercury present and future concerns. Environ. Health Perspect. 96, 159 166. Fitzgerald, W.F., Engstrom, D.R., Mason, R.P., Nater, E.A., 1997. The case for atmospheric mercury contamination in remote areas. Environ. Sci. Technol. 32, 1 7. French, K.J., Scruton, D.A., Anderson, M.R., Schneider, D.C., 1999. Inuence of physical and chemical characteristics on mercury in aquatic sediments. Wat. Air Soil Pollut. 110, 347 362. Giusti, L., Yang, Y.-L., Hewitt, C.N., Hamilton-Taylor, J., Davison, W., 1993. The solubility and partitioning of atmospherically derived trace metals in articial and natural waters: a review. Atmospheric Environ. 27A, 1567 1578. Henry, E.A., Dodge-Murphy, L.J., Bigham, G.N., Klein, S.M., 1995a. Modeling the transport and fate of mercury in an urban lake (Onondaga Lake, NY). Wat. Air Soil Pollut. 80, 489 498. Henry, E.A., Dodge-Murphy, L.J., Bigham, G.N., Klein, S.M., Gilmour, C.C., 1995b. Total mercury and methylmercury mass balance in an alkaline, hypereutrophic urban lake (Onondaga Lake, NY). Wat. Air Soil Pollut. 80, 509 518. Honeyman, B.D., Santschi, P.H., 1988. Metals in aquatic systems. Environ. Sci. Technol. 22, 862 871. Horowitz, A.J., Lum, K.R., Garbarino, J.R., Hall, G.E.M., Lemieux, C., Demas, C.R., 1996. Problems associated with using ltration to dene dissolved trace element concentrations in natural water samples. Environ. Sci. Technol. 30, 954 963. Hakanson, L., 1986a. Projektplan 1985 1989. Projekt Kalkn ing-Kvicksilver. (Project plan 1985 1989. Project Liming Mercury), Nat. Swed. Env. Prot. Board, Solna, SNV Report 3097, 29 p. (In Swedish) Hakanson, L., 1986b. Arbetsplan 1985 1989. Projekt Kalkn ing-Kvicksilver. (Working plan 1985 1989. Project Liming Mercury), Nat. Swed. Env. Prot. Board, Solna, SNV Report 3099, 107 p. (In Swedish) Hakanson, L., 1996a. A simple model to predict the duration of the mercury problem in Sweden. Ecol. Model. 93, 251 262. Hakanson, L., 1996b. Metals in lakes: eld and modeling results on remedial strategies with a focus on mercury and radiocesium. In: Reuther, R. (Ed.), Geochemical Approaches to Environmental Engineering of Metals. Springer, Berlin, p. 221. Hakanson, L., 1999. Water Pollution Methods and Criteria to Rank, Model and Remediate Chemical Threats to Aquatic Ecosystems. Backhuys Publishers, Leiden, p. 277. Hakanson, L., Jansson, M., 1983. Principles of Lake Sedimen tology. Springer, Berlin, p. 316.

clusters of statistically and functionally related variables) would be approximately the same.

Acknowledgements Prof. Lars Hakanson is gratefully acknowl edged for providing data and reviewing the manuscript. An anonymous reviewer is also acknowledged for constructive suggestions, which has improved the content of the paper.

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