Geochemical Journal, Vol. 39, pp.

273 to 284, 2005

Buffering of sodium concentration by cation exchange in the groundwater system of a sandy aquifer
KANGJOO K IM1* and SEONG -TAEK Y UN2
1

Department of Environmental Engineering, Kunsan National University, Jeonbuk 573-701, Korea 2 Department of Earth and Environmental Sciences, Korea University, Seoul 136-701, Korea (Received May 10, 2004; Accepted December 13, 2004)

The water chemistry data obtained from a sandy aquifer in the Trout Lake basin of northern Wisconsin, USA were reinvestigated in order to explain the chemical behavior of sodium concentration in groundwater. Monovalent cations such as sodium and potassium dissolved in groundwater generally remain within narrow concentration ranges. In contrast, calcium and magnesium concentrations show continuously increasing trends due to continuous weathering of aquifer materials, of which reactive minerals are dominated by sodic plagioclase. The similar trend observed in groundwaters contaminated with NaCl-deicer suggests that this unusual chemical behavior of monovalent cation is caused by cation exchange reactions. In other words, when Na ions are introduced into the groundwater system, only a minor fraction of the Na ion (~5%) partitions into the aqueous phase, whereas the majority replaces divalent cations adsorbed on the exchangeable sites of the sediments. However, the cation exchange capacity (CEC) measured for the sandy sediment (~4 meq/kg) is insufficient to cause the observed consistent Na concentration under a batch condition (stagnant groundwater with no molecular diffusion) of cation exchange. Results of transportive exchange calculations suggest that Na concentration can be effectively buffered as the NaCl-contaminated groundwater flows even when the CEC was very low (1 meq/kg) because flowing groundwater can interact with more cation exchange sites than that under stagnant conditions. It is also suggested that the buffering of Na concentration due to cation exchange can partly explain the Ca-excess problem that has been noted previously in the study area.
Keywords: cation exchange, transport, concentration buffering, sodium, Ca-excess problem, mass balance

INTRODUCTION From the standpoint of reactivity and abundance, plagioclase is the most important mineral regulating the chemistry of natural waters in silicate aquifers and watersheds (e.g., Garrels and Mackenzie, 1967; Mast et al., 1990; Kim, 2002). Previous studies have reported that the Ca/Na ratio in water is generally higher than that of plagioclase (Miller, 1961; Garrels and Mackenzie, 1967; Clayton, 1988; Creasey et al., 1986; Mast et al., 1990; Kenoyer and Bowser, 1992a; Kim, 1999). Bowser and Jones (1993) described the lack of agreement between Ca/Na ratios in water and plagioclase as the Ca-excess problem. Several explanations have been suggested for this phenomenon. A watershed-based study carried out in a Precambrian, granitic-metamorphic complex (Colorado, USA) by Mast et al. (1990) suggested that disseminated, microcrystalline calcite grains cause the increased Ca/Na ratios in the watershed streams. However, such small, disseminated
*Corresponding author (e-mail: kangjoo@kunsan.ac.kr) Copyright 2005 by The Geochemical Society of Japan.

calcite grains should have already been dissolved out from the surfaces of the parent rocks if they were exposed to the water because the dissolution rate of calcite is generally six orders of magnitude faster than that of aluminosilicate minerals under neutral pH (Lasaga, 1984). Mast et al. (1990) explained this apparent contradiction by suggesting that the mechanical weathering in the area of higher slopes would continuously expose enough fresh rock surfaces containing calcite grains. However, even if microcrystalline calcite is included within other mineral grains, such an explanation cannot be successfully applied to the Ca-excess problem observed in the groundwater system of a flat area where mechanical weathering is not likely (e.g., Kim, 1999). Others have suggested that the Ca-excess phenomenon is the result of the incongruent release of calcium due to selective dissolution of calcium-rich portions within the zoned plagioclase grains (Clayton, 1988). In contrast, the calcium excess is observed even in cases where no compositional zoning of plagioclase has been observed (e.g., Mast et al., 1990). Kenoyer and Bowser (1992b) explained groundwater chemistry showing Ca-excess phenomenon based on plagioclase weathering associated with precipitation of Na-smectite (i.e., incongruent dissolution of plagioclase).
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Table 1. Statistical summary of the water chemistry data in the Crystal Lake area and in the Sparkling Lake area
pH Crystal Lake area Kenoyer (1986), n = 26* Alk Cl SO4 54.1 187 101 30.9 5.29 375 108 60.0 Ca Mg Na K

min max ave std min max ave std

5.59 8.40 6.49 0.80 5.33 8.35 6.36 0.80

42 1121 371 303 44.4 848 309 204

8.46 381 44.0 88.6 8.63 54.0 20.3 9.66

54.9 958 290 248 61.2 425 197 98.1

24.7 411 144 121 23.7 288 117 74.4

17.4 126 61.2 29.5 22.6 148 60.0 21.2

7.67 38.4 17.0 5.69 9.05 96.9 20.6 15.4

Kim (1996), n = 80

Sparkling Lake area (Krabbenhoft, 1988) Cl < 2 ppm, n = 88 min 5.58 max 7.69 ave 6.79 std 0.49 Cl 2 ppm, n = 221 min max ave std min max ave std 5.55 8.46 6.98 0.71 5.55 8.46 6.93 0.66

212 2295 908 522 173 2660 1053 552 173 2660 1012 547

9.03 55.3 28.0 13.4 56.4 6180 702 1060 9.03 6180 510 946

0.0 282 108 106 0.21 321 106 80.3 0.0 321 107 88.2

190 1605 601 353 47.9 2327 848 442 47.9 2327 777 433

93.0 674 304 164 30.4 1382 433 246 30.4 1382 396 233

35.2 173 93.3 35.4 52.2 4954 537 823 35.2 4954 410 724

8.95 80.1 29.7 19.1 6.14 90.0 31.0 16.2 6.14 90.0 30.6 17.0

Total, n = 309

Units are eq/L except for pH. Minminimum, maxmaximum, aveaverage, stdstandard deviation. *Sampled during 1982. Sampled during 199395. Sampled during 198183.

However, this explanation is not likely because divalent cations such as Ca2+ and Mg 2+ are more favorable to exchangeable sites than monovalent cations such as Na+ and K + in the freshwater system (Sayles and Mangelsdorf, 1979; Drever, 1997). Therefore, Ca-smectite is a more probable secondary phase than Na-smectite in the freshwater system of low Na concentration. The Ca-excess problem observed in the Trout Lake basin, northern Wisconsin, USA, is somewhat different from the reports of previous studies (Kim, 1999). The groundwater of this area shows a more serious Ca-excess phenomenon as the groundwater flows through the sandy aquifer, where plagioclase grains are dominated by sodic compositions, owing to rarely increasing Na concentrations. It is therefore likely that the explanations suggested from previous studies are inappropriate for the calcium problem observed in the groundwater system of the Trout Lake basin. Results of this study suggest that the continuously increasing Ca-excess problem may be associated with concentration buffering for monovalent cations (Na +, K +) in groundwater by cation exchange. In this
274 K. Kim and S.-T. Yun

study, we will address this phenomenon by discussing chemistry data obtained from Trout Lake basin, northern Wisconsin (Kenoyer, 1986; Krabbenhoft, 1988; Kim, 1996; Fig. 1; Table 1) together with mass balance and cation exchange calculations. TROUT LAKE BASIN Trout Lake is located in northern Wisconsin, USA (Fig. 1a). In the basin of Trout Lake, there are many topographically closed depressions that contain lakes and wetlands. The surface aquifer in this area consists of 40 to 60 m thick unconsolidated glacial sediments of Pleistocene age, which overlie Precambrian crystalline bedrocks (Okwueze, 1983). Because the aquifer is dominated by sand-sized materials (85 to 95%) with lesser amounts of gravel (about 5%) and silt/clay (4 to 6%; Kenoyer 1986; Kim 1996), lakes are hydraulically well connected to the groundwater system. A mineralogical investigation by Kim (2002) indicates that the sandy aquifer is mostly composed of quartz (75 to 85%) and K-

freezing point of water to melt ice (NRC, 1991; Keating, 2001; Wegner and Yaggi, 2004). Due to the influence of NaCl-deicers, some groundwaters and lakes located near the highways of the study area show higher Cl and Na levels than others (Bowser, 1992; Krabbenhoft, 1988; Kenoyer and Bowser, 1992a). This will be further discussed in the following subsections. Crystal Lake area Previous studies by Kenoyer (1986) and Kim (1996) were carried out in the isthmus between Crystal Lake and Big Muskellunge Lake (Fig. 1b). The area lies within a state recreational area that was established after relocation of a local highway that ran through the isthmus until approximately 1960. Groundwater flows from Crystal Lake through the isthmus aquifer toward Big Muskellunge Lake. Studies by Kenoyer (1986) and Kim (1996) utilized a total of 28 piezometer wells that were installed along a flow line from Crystal Lake to Big Muskellunge Lake (Fig. 1b). These wells were installed during 1981 82 and were first sampled by Kenoyer (1986) during July 1982. More than 10 years later, Kim (1996) sampled those wells three to four times during 199395. Kenoyer s chemical analysis data show anomalously high Cl concentrations in groundwater samples collected from two wells (K5, K82; Table 2) among the 28 wells. These two wells were placed into approximately the lowest hydrologic end of the isthmus aquifer (Fig. 1b). Kenoyer and Bowser (1992a) interpreted this observation as a relict of NaCl-deicers formerly applied to the old highway. Deicers have not been applied on the isthmus following the establishment of a recreational area. The chemical data obtained from the same wells by Kim (1996) no longer show any indication of the former roadsalt application (Tables 1 and 2), suggesting that the last residues of deicing salt have been completely flushed from the isthmus aquifer. Krabbenhoft et al. (1992) delineated a groundwater flowpath in the area based on oxygen isotope analysis of groundwater samples collected from those wells. A more detailed refinement of the flowpath was carried out by Kim (1996) after installation of an additional multilevel sampler having 12 sampling ports at the center of the isthmus (not shown in Fig. 1b). According to Kim (1996), wells K87, K70, K71, K77, and K5 are located nearly on the same flowpath of groundwater coming from Crystal Lake; hence, can be used to inspect the geochemical evolution of groundwater as groundwater flows through the aquifer. Sparkling Lake area During 1981 to 1983, Krabbenhoft (1988) periodically measured the chemistry of groundwaters from a total of 41 piezometers installed around Sparkling Lake (Fig. 1).

Fig. 1. Location of the Trout Lake basin in Wisconsin, USA (a), and the cross-section of the isthmus between Crystal Lake and Big Muskellunge Lake (b). The solid circles, the numbered lines, and the solid arrow in (b) represent water sampling points, equipotential lines, and the flowpath delineated by Kim (1996), respectively.

feldspar (7 to 15%). Clay minerals (4 to 6%), plagioclase feldspar (2.8 to 3.3%), amphibole (0.8 to 1.2%), chlorite (0.7 to 1.4%), epidote (0.4 to 1.4%), pyroxene (0.2 to 1.4%), and biotite (tr.) comprise only a minor fraction. Plagioclase compositions vary from An 0 to An 80 in anorthite fraction with albite (An 010) and oligoclase (An1030) compositions the most abundant (82%). Grains of calcic plagioclase (above An50) are rarely observed (5%) and the average composition of the plagioclase is An18 (Kim, 2002). Carbonate minerals (e.g., calcite) have not been identified in any of the sediments in the study area (Kenoyer, 1986; Keating, 1995; Kim, 2002). There are several local highways running through the study area (Fig. 1a) and road salts are applied on the highways as a deicing agent during winter (Krabbenhoft, 1988; Bowser, 1992; Kenoyer and Bowser, 1992a). The most commonly used deicing salt in USA, including this area, is sodium chloride (NaCl; rock salt) because it is readily available, inexpensive, and effectively depresses the

Buffering of sodium concentration by cation exchange 275

Table 2. Water chemistry of the wells K5 and K82. K5G and K82G are the data obtained by Kenoyer (1986) during July 1982. K5K and K82K are the averages of three- to four-time measurements during 1993 to 1995 by Kim (1996)
Sampling date K5G K5K K82G K82K July 82 9395 July 82 9395 pH 7.46 7.73 7.28 7.13 Alk 624 636 717 628 Cl 381 13 299 43 Ca 604 391 609 378 Mg 395 263 411 274 Na 78 63 83 74 K 20 12 15 14 SO4 83.3 68.1 97.8 75.9

Units are eq/L except for pH.

Among the 309 groundwater samples collected from those wells, 71% ( n = 220) showed Cl concentrations higher than 2 mg/L (56 mol/L) and 28% (n = 87) showed Cl levels exceeding 10 mg/L (282 mol/L; Table 1). In contrast, the highest Cl concentration in the Crystal Lake area was only 1.91 mg/L (54 mol/L; Table 1) based on the measurements performed when the road salt effect is no longer observed (Kim, 1996). The higher Cl concentrations in the Sparkling Lake area also have been attributed to the application of deicing salt (NaCl) on the nearby local highways (Fig. 1a) during winter (Krabbenhoft, 1988). Considering water data for groundwater in the Crystal Lake area measured during 1993 95 by Kim (1996), the sea-spray effect causes Cl concentration of 2 mg/L in maximum for groundwater of Trout Lake basin. Therefore, it is inferred that Cl levels higher than 2 mg/L in the study area reflect the influence of road salt application. Because of the road salt application, Sparkling Lake shows a chemical trend where Na and Cl concentrations are continuously increasing over time (Bowser, 1992). Interestingly, however, the Cl concentration increase is more significant than that of the Na concentration. To explain this phenomenon, Bowser (1992) postulated that the loading of NaCl-rich snowmelt into the aquifer possibly stimulates ion-exchange reactions, which releases weakly held Ca and Mg into the groundwater. However, the buffering effect of the cation exchange was not considered by Bowser (1992) because he focused only on the temporal trend of the water chemistry of Sparkling Lake. Ca-EXCESS PROBLEM IN THE S TUDY AREA The Ca-excess problem was also reported in the sandy aquifer between Crystal Lake and Big Muskellunge Lake by Kim (1999). According to Kim (1999), groundwater of the area showed Ca/Na molar ratios (0.3 to 4.4 with an average of 1.83 and a standard deviation of 0.82) that are much higher than predicted from the dissolution of plagioclase grains. The Ca/Na ratio predicted from the average plagioclase composition (An18; Kim, 2002) is
276 K. Kim and S.-T. Yun

Fig. 2. Variation of Ca/Na molar ratio in groundwaters along a flow path from the Crystal Lake (C.L.) (Fig. 1b; Kim, 1996). Note that the Ca/Na ratio increases continuously as groundwater flows from Crystal Lake to well K5. Error bars indicate +/ one standard deviation. Arrows A and B represent Ca/Na molar ratios expected from average plagioclase composition (An18; Kim, 2002) and predicted from dissolution kinetic data of plagioclase minerals for different compositions (Mast and Drever, 1987; Oxburgh et al., 1994), respectively.

only 0.22 (Fig. 2). Because some calcic plagioclase grains, which are more reactive than sodic plagioclase grains (Busenburg and Clemancy, 1976; Lasaga, 1984; Clayton, 1988; Oxburgh et al., 1994; Stillings and Brantley, 1995), are also observed in the study area, the prediction of Ca/ Na ratio just based on average composition may not be appropriate. Therefore, we re-estimated the Ca/Na ratio based on the reported dissolution kinetics and the relative compositional abundances of plagioclase grains. For this, the kinetic data estimated from the lab experiments by Dr. Drever s research group (Mast and Drever, 1987; Oxburgh et al., 1994) were used. They carried out several dissolution experiments using fluidized bed reactors for plagioclase having different compositions; therefore, their data allow the prediction of cation release rates from plagioclase grains of various compositions. The Ca/Na molar ratio expected from these kinetic data is 0.57, which

Fig. 3. Plots of NaCl-corrected, total cation (Ca + Mg + Na + K Cl in eq/L; a), Ca + Mg (b), and Na + K (c, d) as a function of alkalinity for groundwater samples from the Sparkling Lake area (solid circle; Krabbenhoft, 1988) and those from the Crystal Lake area (open circle; Kim, 1996). (d) is an enlarged detail of the lower Na + K levels in (c).

is somewhat higher than that expected from the average plagioclase composition (0.22) but is still much lower than that observed in the groundwater (1.83 in average). This result suggests that preferential dissolution of calcic plagioclase does not fully explain the Ca-excess problem observed in the study area. An interesting feature observed in the study area is that the Ca-excess problem becomes more significant as groundwater reacts with aquifer materials for a more prolonged time (Fig. 2). Figure 2 shows the Ca/Na ratios for groundwater samples collected from the wells located on a flowpath from Crystal Lake (Fig. 1a; Kim, 1996). The figure shows continuously increasing Ca/Na values as groundwater flows through the aquifer. We prepared plots of various cations as a function of alkalinity, a reaction progress variable for mineral weathering (Plummer et al ., 1983; Kim, 2003), to analyze the behavior of each cation as the mineral-water interaction progresses (Fig. 3) and, thus, to figure out the causes for the observed Ca/Na ratio trend in groundwater (Fig. 2). The 1:1 equivalent relation between Ca + Mg + Na + K Cl and alkalinity (Fig. 3a) suggests that mineral weathering is the major source of the total cation concentration if the effects of Cl-salts (deicer, sea spray) were eliminated from the observed water chemistry (Kim, 2002, 2003). Here, Ca + Mg + Na + K Cl represents the total cation concentration (Ca + Mg + Na + K in equivalence) corrected for that contributed from Cl-salts by assuming that both deicer and seawater have approximately 1:1 equivalent relation between Cl and total cations. In fact, the to-

tal cation to Cl equivalent ratio in seawater is slightly higher than one (~1.1; Stumm and Morgan, 1995). However, this much of a difference may not cause significant errors for those corrections because the sea spray effect in the study area is expected to be very small (2 mg/L in maximum) based on the Crystal Lake area data obtained during 199395 (Table 1). Because of the mineral weathering, concentrations of divalent cations (Ca + Mg) also show a continuously increasing trend as alkalinity increases (Fig. 3b). On the other hand, concentrations of monovalent cations (Na + K) seldom increase after reaching a certain concentration level, especially for the case of Kims Crystal Lake area data (Figs. 3c and 3d). Due to the unusual behavior of monovalent cations, the Ca/Na ratio of groundwater continuously increases and the Ca excess becomes more prominent as groundwater progressively reacts with aquifer materials (Fig. 2). It is noteworthy that Sparkling Lake area data also generally follow the similar trend of Na + K concentration that is observed in the Crystal Lake area (Figs. 3c and 3d). This suggests that concentrations of monovalent cations in groundwater of both areas are regulated by a similar process, even though groundwater chemistry in the Sparkling Lake area is significantly influenced by the application of NaCl-deicer. Explanation of the observed Ca-excess simply based on mineral dissolution seems unlikely because the increase of calcium concentration without sodium (Figs. 2, 3c and 3d) would require little or no dissolution of plagioclase, the most abundant reactive mineral in the sandy aquifer of the study area (Kim, 2002), while other silicate minerals have to be dissolved to continuously increase the alkalinity. However, the calculated mineral saturation indices (7.5 to 2.0; Bullen et al., 1996; Kim, 1999) suggest undersaturation with respect to plagioclase. Therefore, an alternate explanation is required for the Caexcess problem observed in the study area. Uptake of sodium by exchange is suggested. CATION E XCHANGE CAPACITY OF THE SEDIMENTS To measure the cation exchange capacity (CEC), two sandy sediment samples and two silt samples were collected at depths from 5 to 7 m (sand) and from 13 to 14 m (silt) at the center of the isthmus between the Crystal Lake and the Big Muskellunge Lake (Fig. 1b). Prior to the CEC measurements, the sediment samples were washed with deionized waters and centrifuged, then dried for 12 hours at 105 C. The measurements were carried out by preparing precisely weighed, dried samples (10 g for sand and 1 g for silt) in each 50 ml test tube. Adsorbed cations on the sediments were replaced by adding 40 ml of 1M BaCl2 solution into the test tubes. The tubes were shaken for 5 hours and were centrifuged with 6000 rpm for 30 min-

Buffering of sodium concentration by cation exchange 277

Table 3. Results of the CEC measurements

Ca Sand sample Sample 1 Sample 2 average Silt sample Sample 1 Sample 2 average Mg Na K CEC (sum)

2.57 2.78 2.67

0.89 1.02 0.96

0.07 0.10 0.09

0.19 0.12 0.16

3.72 4.03 3.87

31.9 34.5 33.2

14.6 14.5 14.6

0.3 0.4 0.4

1.5 1.2 1.4

48.4 50.6 49.5

Fig. 4. Plot of sodium with respect to chloride for the groundwater samples of the Sparkling Lake area (Krabbenhoft, 1988). (b) is a detail of the shaded area in (a).

Units are meq/kg.

utes. The supernatants were gently poured into glass bottles washed with 20% HCl solutions and were filtered with 0.45 m membrane filters. The filtrates were analyzed using an atomic absorption spectrophotometer (UNICAM 930) for Ca, Mg, Na, and K. These CEC measurement procedures were duplicated for each sample. The results show that the sand and silt sediments in the study area have CEC values of 3.9 meq/kg and 49.5 meq/kg, respectively (Table 3). The CEC values for sandy sediment samples are somewhat lower than those reported in other glacial outwash deposits (~10 meq/kg; Bjerg and Christensen, 1993). The results also show that divalent cations such as Ca and Mg occupy most of the exchangeable sites in the sediment (94% for sand, 96% for silt; Table 3). In contrast, the fractions of monovalent cations such as Na and K in the exchangeable sites were only about 5%. The cation fractions observed in this study are generally comparable to those reported for sediments or soils in equilibrium with freshwater (Sayles and Mangelsdorf, 1979; Czepinska-Kaminska et al., 2003; Kariuki and van der Meer, 2004). BUFFERING OF Na AND K CONCENTRATIONS BY C ATION EXCHANGE As described earlier, groundwater samples collected from wells K5 and K82 in the Crystal Lake area showed very high chloride ion concentrations during July 1982 due to road salts applied on the old highway which previously existed on the isthmus (Kenoyer, 1986; Table 2). Inspection of Kenoyer s data for those wells (Table 2) reveals that the sodium concentrations were not balanced by chloride concentrations and remained at levels comparable to those of nearby uncontaminated wells (60 to 75 mol/l; Kenoyer, 1986; Kim, 1996). Kenoyer s data for these wells showed calcium and magnesium concentrations much higher than those observed 11 to 13 years later when the residues of deicing salts have been completely flushed (Kim, 1996). In contrast, both data show

monovalent cation concentrations (Na+, K+) that are not significantly different from each other (Table 2). Sodium in the groundwater around Sparkling Lake exhibits similar behavior (Fig. 4). In the Sparkling Lake area, Na concentration falls within a narrow concentration range while Cl concentration varies widely when solute concentrations are low (Cl < 400 eq/L; Fig. 4). The chemical behavior of sodium may suggest that sodium concentration is strongly buffered by cation exchange in the groundwater system. In other words, most of the sodium ion introduced into the groundwater system is used for replacement of Ca and Mg ions adsorbed onto the exchangeable sites of sediment; thus the actual increase in Na concentration by NaCl addition is only small and sometimes non-recognizable. To investigate this hypothesis, mass balance and cation exchange calculations were performed for the two road-salt contaminated groundwaters in the study area. Mass balance analyses For convenience, the chemistry data reported by Kenoyer (1986) for the wells K5 and K82 are denoted as K5G and K82 G, and those measured by Kim (1996) are designated as K5K and K82 K in this paper. To carry out mass balance calculations, two assumptions were made: (i) the background water chemistry of wells K5 and K82 prior to the road-salt contamination were the same as the water chemistry observed by Kim (1996) and (ii) the differences in chloride concentration between the two studies (369 mol/l for K5 and 256 mol/l for K82) correspond to the amount of road salt (NaCl) introduced into those wells. If increased Na ions in groundwater by NaCl introduction induce a cation exchange reaction replacing other cations adsorbed on exchangeable sites, the sodium loss from groundwater due to cation exchange (a in eq/L) has to be balanced by the concentration increase of other cations (b in eq/L), as shown in the following equations. (ClG ClK) (Na G NaK) = a (1)

278 K. Kim and S.-T. Yun

Table 4. Results of mass balance calculations for K5 and K82

K5 AlkG AlkK (ClG ClK ) (Na G Na K ) = a (Ca G Ca K ) + (MgG MgK ) + (KG KK ) = b Mass balance error = ( b a)/( b + a) 12 353 353 0% K82 89 248 369 ( 280*) 20 ( 6*)%

Units are eq/L. Subscripts G and K represent the concentrations measured by Kenoyer (1986) in 1982 and those by Kim (1996) during 1993 95, respectively. *After correction of the well-drilling effect suggested by Kim (2003).

(MgG Mg K) + (CaG CaK) + (KG KK) = b

(2)

for wells K5 and K82 are not applicable. Instead, a mass balance analysis based on bulk data for the road-salt contaminated groundwaters (Cl 2 mg/L) was performed. To work out background Ca + Mg + K levels before contamination, we first analyzed the equivalent relationship between Ca + Mg + K and alkalinity for the groundwaters not affected by road salt application (Cl < 2 mg/L; Fig. 5a). Figure 5a shows that Ca + Mg + K is linearly related with alkalinity with r2 value of 0.96 when the roadsalt effect is negligible. We assumed that Ca + Mg + K values for groundwaters with Cl 2 mg/L would also have shown the same relation in Fig. 5a with respect to alkalinity, if they were in the background state before contamination. The increased Ca + Mg + K concentration by deicer contamination can be calculated from the equation: Ca + Mg + K (0.93 alkalinity + 89.6) ( eq/L). (3)

where the subscripts G and K also indicate the concentrations reported by Kenoyer (1986) and Kim (1996), respectively. The results of mass balance calculations are illustrated in Table 4. The mass balance error for well K5 is negligibly small, suggesting that the higher Ca and Mg concentrations in Kenoyer s data were the results of sodium uptake by cation exchange. In contrast, the calculation for well K82 shows a relatively large error (20%). Considering the much higher alkalinity in K82G than that in K82K, the larger mass balance error for the well K82 may be the result of the enhanced weathering caused by drilling as described by Kim (2003). Because of this drilling effect, many of the groundwater chemistry data collected by Kenoyer (1986) showed higher alkalinity, and Ca and Mg concentrations than those observed more than 10 years later by Kim (1996). Kim (2003) reported that higher solute concentrations could be derived shortly after well installation due to rapid dissolution of newly exposed mineral surfaces and hyperfine mineral grains, which are inevitably created during the well drilling process. K5 was installed one year earlier (1981) than K82 (1982; Kim, 2003); thus, most of the solutes generated by drilling in K5 may have been flushed by the time the first sampling was performed in 1982. The difference between AlkG and AlkK (89 eq/L for K82) can be attributed to excess cation concentration related to the drilling-enhanced weathering because alkalinity increases equivalently with total cation during weathering and is not influenced by cation exchange and/or salt dissolution (Kim, 2003). When the contribution from the drilling effect is corrected for K82G, b becomes 280 (=369 89) eq/L, which is similar to a (=248 eq/L) and results in 6% of mass balance error. We also carried out a mass balance analysis for the deicer-contaminated groundwaters in the Sparkling Lake area. However, water chemistry data in the background condition before contamination are unavailable in this case. Therefore, the method of mass balance analyses used

A good linear relationship with a slope of one (r2 = 0.93; Fig. 5b) between the Na loss after the NaCl input (=Cl Na; eq/L) and the cations over-increased (Eq. (3)) implies that both are well balanced. This also suggests that most of the Na ions introduced into the groundwater as a form of NaCl deicers were used for replacement of other cations adsorbed onto the sediment, as was observed for the deicer-contaminated wells in the Crystal Lake area (K5 and K82). The slight displacement of the linear relation from the origin in Fig. 6b (intercept = 104.7 eq/L) may be the result of Na ions contributed from mineral weathering because all the Na ions in groundwater were assumed to have originated from NaCl deicers in this mass balance analysis. In addition, some groundwaters showing negative values (Fig. 5b) are likely to be related with the flushing of the deicer-contaminated sediment with low ionic strength groundwaters (Appelo, 1994). If the aquifer was originally in equilibrium with waters of high Na concentration, cation exchange reactions replacing Na by Ca or Mg could occur while this sediment is being flushed with fresh groundwaters. Cation exchange under a batch condition To check whether the cation exchange reaction suggested from the mass balance analysis is thermodynamically valid, equilibrium concentrations after the deicer contamination for well K5 were also calculated using a geochemical code, PHREEQC (Parkhurst and Appelo, 1999). The calculations were carried out based on CEC values varying widely from 0 to 200 meq/kg (Table 5a) so that we can see the effect of CEC on concentration buffering. Given that groundwater fills the pore of the sediment (porosity = 0.35 on average; Kim et al., 1999) and the density of sediment grains is about 2.7 g/cm3, the CEC range considered during these calculations is equiva-

Buffering of sodium concentration by cation exchange 279

Fig. 5. Relationship between alkalinity and Ca + Mg + K for groundwaters unaffected by road salt (Cl levels <2 mg/L, Sparkling Lake area data; Krabbenhoft, 1988) (a), and the mass balance analysis result for groundwaters significantly influenced by road salts in the Sparkling Lake area (Cl level 2 mg/L; Krabbenhoft, 1988) between Na not increased (=Cl-Na) and other cations (Ca, Mg, K) over-increased after the influence of road salt (b). Over-increased Ca + Mg + K was calculated by assuming that the NaCl-contaminated groundwaters would show the same relationship shown in (a) before contamination.

Table 5. Summary of various cation exchange calculations using PHREEQC (Parkhurst and Appelo, 1999)
a) Cation exchange under a batch condition (Fig. 6) 1. Physical condition: stagnant groundwater with no diffusion (batch condition) 2. Initial water chemistry: K5K (Table 2) 3. Input NaCl: 369 mmol per liter of groundwater 4. CEC: 040 meq/kg (0200 meq of exchanger per liter of groundwater; initially in equilibrium with K5K ) 5. Thermodynamic data: PHREEQC data base b) Cation exchange under a flowing condition (Fig. 7) 1. Physical condition: Advective transport of a liter of contaminated groundwater 2. Initial water chemistry: K5K (Table 2) 3. Input NaCl: 369 mmol per liter of groundwater 4. CEC: 1, 4, 50 meq/kg (5, 20, 200 meq of exchanger per liter of groundwater; initially in equilibrium with K5K ) 5. Thermodynamic data: PHREEQC data base 6. Number of cells: 40 7. Pore volume of each cell: 1 liter 8. Total volume of each cell: 2.86 liter c) Cation exchange under a flowing condition (Fig. 8) 1. Physical condition: Advective transport of a liter of contaminated groundwater 2. Initial water chemistry: K5K (Table 2) 3. Input NaCl: 50 mmol, 3 mmol per liter of groundwater 4. CEC: 4 meq/kg (20 meq of exchanger per liter of groundwater; initially in equilibrium with K5K ) 5. Thermodynamic data: PHREEQC data base 6. Number of cells: 40 7. Pore volume of each cell: 1 liter 8. Total volume of each cell: 2.86 liter

lent to a situation that a liter of groundwater interacts with 0 to 1000 meq of exchangers (Table 5a). For this calculation, we assumed that (i) the exchangers of the sediments were originally in equilibrium with the groundwaters of K5K before road-salt contamination and (ii) K5G was the result of 369 mol/L of NaCl being introduced. Precipitation of mineral phases possibly caused by the introduc-

tion of NaCl was not considered during the calculation because the results did not indicate any significant changes in saturation status for the potential secondary mineral phases by the NaCl input. The results of exchange calculation show a poor agreement with the observed water chemistry (K5G) at the CEC value equal to that measured for the sand samples (4 meq/

280 K. Kim and S.-T. Yun

Fig. 6. Exchange calculation results using PHREEQC (Parkhurst and Appelo, 1999) for batch conditions of adding 369 mol of NaCl into one liter of groundwater that is in contact with sediments having CEC values from 0 to 200 meq/kg. See Table 5a for more details of this calculation.

kg; Fig. 6). In contrast, the results become very close to the observed values when CEC values are higher than 200 meq/kg. However, such an abnormally high CEC value is not realistic in natural environments (Sposito, 1989; Drever, 1997). Despite the fact that the exchange calculation failed to match the observed water chemistry, the results strongly suggest that the buffering of monovalent concentrations could be possible if the contaminated groundwater can interact with more exchangers. We surmised that the discrepancy between the CEC values measured from the sand samples (Table 3) and those predicted from above calculation (>100 meq/kg; Fig. 7) were the results of the fact that the calculation does not appropriately mimic the real situation. Those calculations only considered a batch experiment-like situation; that is, simply adding 369 eq of NaCl into a liter of stagnant groundwater that is in contact with exchangeable sites of the sediment. In the real situation, however, groundwater is continuously flowing through the aquifer. Consequently, the contaminated groundwater can encounter more exchangers than those expected from the batch experiment-like condition. To confirm this hypothesis, other cation exchange calculations were carried out considering groundwater movement in the aquifer. Cation exchange under a transport condition In this calculation, one liter of NaCl-contaminated groundwater (K5K + 369 mol of NaCl) is allowed to flow through the aquifer and the concentration changes as the groundwater travels were continuously calculated (Table 5b). For this, a 1-D advective transport model, which considers cation exchange reactions, was developed using PHREEQC (Parkhurst and Appelo, 1999). To

Fig. 7. Results of transportive exchange simulation using PHREEQC (Parkhurst and Appelo, 1999) for one liter of groundwater (K5 K) contaminated with 369 mol of NaCl. Simulations were performed for CEC values 1 (a), 4 (b), and 50 meq/kg (c). See Table 5b for more details of this calculation. Note that all the results show the similar patterns; that is, water chemistry of the contaminated groundwater becomes closer to the observed water chemistry (K5G) and finally reaches a steady state as the groundwater flows. However, a transport of more cells is required when the CEC of the sediment is low.

see concentration changes of the NaCl contaminated groundwater solely by cation exchange, dispersion was not considered in this calculation. The effect caused by dispersion will be discussed later. The model has 40 cells and each cell is assumed to have a liter of groundwater filling the pore of the sediment. Therefore, each cell has a volume of 2.86 liters. Exchanger concentrations of each cell are uniform and were calculated from the given CEC values by assuming that porosity and grain density of the sediments are 0.35 (Kim et al., 1999) and 2.7 g/cm3, respectively. The simulations were performed for the CEC
Buffering of sodium concentration by cation exchange 281

Fig. 8. Results of transportive exchange simulation using PHREEQC (Parkhurst and Appelo, 1999) for one liter of groundwater (K5 K) contaminated with NaCl 50 mol (a) and 3 mmol (b). CEC of the sediment is assumed to be 4 meq/kg. See Table 5c for more details of this simulation. Note that transport of more cells is required to reach a steady state when the groundwater is contaminated with larger amount of NaCl.

values of 1, 4, and 50 meq/kg. The sediments in each cell were initially in equilibrium with groundwater of background water chemistry (K5K; Table 2). The simulation results are presented in Fig. 7. The results show that the concentration of Na (or Ca and Mg) continuously decreases (or increase) as the NaCl-contaminated groundwater flows through the aquifer and finally reaches a steady state where the concentrations of each cation are nearly the same as the observed water chemistry (K5G). All simulation results with various CEC values show the same results except for the number of cells required to travel to arrive at a steady state. In the case of the simulation using the measured CEC values for sands (4 meq/kg), the simulated water chemistry becomes the same as K5G when the NaCl contaminated groundwater travels about 15 cells. The number of cells required to reach K5G is greatly reduced (about 2 cells) when the CEC value was equivalent to that of silts (50 meq/kg). However, for the case of the simulation with very low CEC value of 1 meq/kg, which is a quarter of that for the sand in the study area, the contaminated groundwater has to flow more than 40 cells before it reaches a steady state.
282 K. Kim and S.-T. Yun

Additional transportive exchange calculations were performed to see the effect of NaCl input amounts (Table 5c). The calculations were carried out for 50 mol and 3 mmol of NaCl inputs into a liter of groundwater and the CEC values were fixed to 4 meq/kg. All other conditions are the same as those for Fig. 7b. Similarly to the results for the calculation with different CEC values (Fig. 7), the calculation results show that most of the Na introduced as NaCl is eventually used for the replacement of divalent cations adsorbed on the sediment in all NaCl input conditions (Fig. 8). As a result, the increases in Na concentration are very small relative to the input amounts after the attainment of a steady state. However, the groundwater has to travel more cells to reach a steady state and the Na concentration at the steady state becomes higher as the input amount of NaCl increases. Na concentration at the steady state increases from 65.2 to 147.1 mol/L when the NaCl input increases from 50 mol to 3 mmol. Based on the above calculations it becomes clear that the monovalent concentrations could be strongly buffered by cation exchange reactions even though the CEC values of the sediments are very low because groundwater can encounter sufficient exchangeable sites as it flows through the aquifer. If we assume that the cross-sectional area of contamination is only 10 cm 10 cm, then the cell length of our calculation is about 29 cm long. This means that a liter of groundwater contaminated with 369 mol of NaCl will reach a steady state showing water chemistry of K5G within a transport of 12 m even when the CEC is extremely low (=1 meq/kg; Fig. 8a). However, the distance required to reach a steady state would be much less than this in the real situation because dispersion was not considered in our calculations. It is well known that dispersion causes reduced concentration peaks and wider concentration plumes as groundwater flows downgradient. Furthermore, a modeling study also reports that the study area shows enhanced dispersions due to fluctuations of recharge rates and lake levels (Kim et al., 2000). Under this condition, the contaminated groundwater will encounter more exchangeable sites as it flows and will show buffering effect of Na concentration more readily than that expected from this calculation. The results of the above calculations strongly suggest that the observed small differences in Na and K concentrations before and after the road-salt contamination are valid thermodynamically and are closely related with groundwater flow and cation exchange. The observation of high Na concentration at high Cl levels (Fig. 5) are likely to be related with the sampling of groundwaters before they reach a steady state, considering the fact that high Na and Cl concentrations are generally observed in the wells located near the local highway, the contamination source (Krabbenhoft, 1988).

CONCLUSIVE REMARKS Based on the results of this study, it becomes clear that Na concentration can be rarely increased by the Na ion input because of transportive cation exchange. A large cation pool in the exchangeable sites on sediment relative to that introduced into groundwater system is suggested as a reason for the observed buffering effect. Considering porosity (0.35) and grain density (2.7 g/cm3) of the sandy sediment, the CEC value of 4 meq/kg is equivalent to the condition that one liter of groundwater interacts with about 20 meq of cations adsorbed on the sediment. Because the highest total cation concentration in groundwater of the Crystal Lake area is only 0.74 meq/L (Kim, 1999), the amount of cations adsorbed onto the sandy sediment is at least 27 (=20/0.74) times more than that dissolved in the groundwater in total. Furthermore, the amount of exchangeable site that a unit volume of groundwater can interact would be increased continuously as the groundwater flows through the aquifer. Under this condition, concentrations of each cation in groundwater can be largely regulated by the cations adsorbed onto the sediment (Drever, 1997). Thus, when some Na ions are introduced into the groundwater system, the added ions will be redistributed between groundwater and sediment by cation exchange to reach a new equilibrium. During this reaction, added Na ions replace the adsorbed divalent cations and the concentration of Na decreases. In addition, in the cation exchange equation between monoand di-valent cations (Drever, 1997) the power is two for monovalent cation while that for divalent cation is one; XD/XM2 = K(mD/mM2) (4)

after an initial increase as groundwater flows from a very dilute water body (Crystal Lake; Fig. 3d) are also partly associated with the buffering effect of cation exchange. Because of the cation exchange and transport, the concentration of sodium ion in groundwater may not increase as much as the supply from the weathering of sodic plagioclase. This seems to be one reason for the observed Ca-excess problem that becomes more serious as groundwater interacts with the aquifer materials for a more prolonged time (Fig. 2).
AcknowledgmentsThis study was financially supported by the NSF-LTER program, by the Saemankeum Environmental Research Center, and by the Environmental Geosphere Research Lab. The authors thank Dr. Carl J. Bowser and Dr. Blair F. Jones for their invaluable discussions on this paper and Mr. Jinsam Kim for his CEC measurements. This paper has been greatly improved because of the comments from Dr. Tasuku Akagi and the two anonymous reviewers.

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