Climate modulates the acidity of Arctic lakes on millennial time scales Alexander P. Wolfe Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, AB T6G 2E3, Canada ABSTRACT High-resolution diatom stratigraphies from two lakes on eastern Baffin Island (Nunavut, Canadian Arctic) are used to reconstruct lake-water pH over the past 5 k.y. Despite contrasting geomorphic histories and markedly different diatom floras, the inferred pH of both lakes declined in concert with Neoglacial cooling. This result confirms that climate exerts a first-order influence on the acidity of these poorly buffered oligotrophic lakes, through links between lake ice cover, primary productivity, and dissolved inorganic carbon dynamics. Diatom-based pH inferences from dilute lakes can therefore assist paleoclimatic interpretations from lake sediments. Keywords: diatoms, lake acidity, Holocene, Neoglacial, Baffin Island. INTRODUCTION The suggestion that climate controls the pH of oligotrophic lakes originated from studies in the Alps (Psenner and Schmidt, 1992; Sommaruga-Wögrath et al., 1997). In these analyses, cold air temperatures induced a lowering of lake-water pH, and vice versa, through links between lake alkalinity and catchment weathering, eolian dust fluxes, lake metabolism, and dissolved inorganic carbon speciation. However, these inferences are based on paleolimnological records limited to the past 200 yr. In most lakes, the apparent relationship between air temperature and pH collapsed once anthropogenic overprinting, in the form of atmospheric deposition of strong-acid anions, came into play during the twentieth century. Therefore, at present there is only tantalizing evidence for the direct coupling of climate and lake-water acidity (Koinig et al., 1998). It is of considerable interest to explore whether climate regulates the acidity of dilute lakes over longer time scales for two reasons. First, lake-water pH can be reconstructed reliably from sediment diatom assemblages (Battarbee et al., 1999). Second, growing interest in climate change is stimulating new approaches at gleaning paleoclimatic information from lacustrine archives, especially in remote regions (Smol and Cumming, 2000). Furthermore, the possibility exists that current changes in the Arctic climate system may alter the chemical regimes of high-latitude lakes, potentially influencing their susceptibility to anthropogenic atmospheric deposition. In this study, high-resolution diatom-inferred lakewater pH histories for the past 5 k.y. are presented from two ultraoligotrophic Arctic lakes. These reconstructions are assessed by comparing them to independent late Holocene paleoclimatic reconstructions. The results suggest that a direct link exists between climate and lake acidity in this environment. REGIONAL LATE HOLOCENE PALEOCLIMATOLOGY There is consensus that the late Holocene was an interval of progressive cooling in the Baffin Bay region, as inferred by isotopic, palynological, and glacial geologic evidence (Fig. 1). Although the area has undoubtedly been subject to submillennial climate variability, the low-frequency component of this cooling appears to be regulated by high-latitude summer insolation. Late Holocene cooling (Neoglacial) culminated in the Little Ice Age ca. A.D. 1450–1850. Thereafter, summer temperatures have increased markedly (Overpeck et al., 1997), partially in response to greenhousegas forcing. STUDY SITES AND CORE CHRONOLOGIES The two investigated lakes are 75 km apart on the north coast of Cumberland Peninsula (Fig. 2). Mean annual temperature is ;210 8C, and total annual precipitation is ;350 mm. Kekerturnak Lake (678539N, 648509W; 120 m above sea level [masl]) occupies a bedrock basin in outer Qajon Fiord and is younger than 9 ka, having been overridden during Late Foxe glaciation (Steig et al., 1998). In contrast, Fog Lake (678119N, 638159W; 460 masl) is perched on an unglaciated upland and preserves a sediment record of at least 90 k.y. (Wolfe et al., 2000). The proximity of the lakes implies they have undergone the same Holocene climate forcing, despite large differences in geomorphic history and age. This facilitates the distinction of purely limnological responses to climate, which should be equally expressed at both sites, from nonclimatic edaphic factors. Regional bedrock geology is Archean granite and gneiss. Both lakes are highly dilute (conductivities ,10 mS·cm21; [Na11 K11 Mg211 Ca21] ,5 mg·L21) and are therefore largely unbuffered. Modern summer epilimnetic pH is 6.32 in Fog Lake and 6.25 in Kekerturnak Lake, whereas HCO32 Figure 1. Summary of late Holocene climatic evolution of Baffin Bay. A: Summer insolation at 658N (thick line) (Berger and Loutre, 1991) and oxygen isotope stratigraphy (SMOW—standard mean ocean water) from Devon Island Ice Cap (Paterson et al., 1977). B: Pollen-based summer temperature departures integrated for Baffin Island, Labrador, and Keewatin (Andrews et al., 1981). C: Time versus distance diagram of glacial activity in Pangnirtung Pass, southern Cumberland Peninsula (Davis, 1985). q 2002 Geological Society of America. For permission to copy, contact Copyright Permissions, GSA, or [email protected]. Geology; March 2002; v. 30; no. 3; p. 215–218; 4 figures; 1 table. 215 Figure 2. Location of study sites on northern Cumberland Peninsula. Open circles show locations of lakes used to develop diatom-based inference models (Joynt and Wolfe, 2001). concentrations are 0.09 and 0.11 mg·L21, respectively. Cores of 35 cm length were collected with a gravity corer (Glew, 1989) and subsampled into continuous 0.5 cm increments in the field. Both cores are composed of massive olivebrown algal gyttja. Each core’s chronology is based on five accelerator mass spectrometry 14C dates from sediment humic acid extracts (Abbott and Stafford, 1996). Humic acid 14C results were corrected by subtracting 300 yr to account for the mean lag associated with the sequestration of terrestrial dissolved organic carbon to the lakes (Miller et al., 1999) and calibrated to calendar years before present (Stuiver et al., 1998). The resulting chronologies produce age versus depth relationships fitted by polynomial solutions (Table 1; Fig. 3, A and B). Figure 3. A and B: Age models for Kekerturnak and Fog lake gravity cores, based on humic acid accelerator mass spectrometry 14C dates. C: Relationship between surface-sediment diatom-inferred pH and measured pH from 61 lake training set. Root-mean-squared error of prediction (RMSE) and bootstrapped RMSE (in pH units) are included. D: Residuals for same relationship, demonstrating absence of bias at either extreme of pH. DIATOM-INFERRED pH RECONSTRUCTIONS Diatom slide preparation, counting, and taxonomy followed standard protocols described elsewhere (Wolfe et al., 2000). A known quantity of markers (Eucalyptus pollen) was added to digested slurries in order to calculate diatom concentrations (Wolfe, 1997). At least 500 diatom valves were counted in contiguous 0.5 cm samples for the entire Fog Lake core and the upper 20 cm of the Kekerturnak Lake core, and every 1.0 cm below 20 cm. Lake-water pH inferences were made by several methods. (1) A regional transfer function was applied to down-core diatom assemblages, based on weighted-averaging (WA) regression and calibration of surface-sediment diatom assemblages and measured limnological parameters from 61 Baffin Island lakes TABLE 1. RADIOCARBON DATES FROM FOG AND KEKERTURNAK LAKE CORES Depth (cm) Kekerturnak Lake 6.5–7.0 13.5–14.0 20.0–21.0 27.0–28.0 34.0–35.0 Fog Lake 6.5–7.0 13.5–14.0 20.5–21.0 27.5–28.0 34.5–35.0 216 Laboratory number 14 C age (yr B.P.) 6s (yr) Corrected age (yr B.P.) Calibrated age (yr B.P.) Range of solutions (62s) CAMS-44438 CAMS-44439 CAMS-44440 CAMS-44441 CAMS-44442 1190 2250 3110 3900 4780 50 50 60 50 50 890 1950 2810 3600 4480 790 1915 2920 3870 5205 675–925 1740–1990 2770–3070 3725–4075 4875–5300 CAMS-44443 CAMS-44444 CAMS-44445 CAMS-44446 CAMS-44447 1230 2080 3030 3720 4560 50 50 50 50 50 930 1780 2730 3420 4260 885 1695 2835 3675 4835 725–940 1550–1820 2755–2940 3485–3825 4645–4870 (Joynt and Wolfe, 2001). In this study, pH emerged as a highly significant variable (Fig. 3, C and D). (2) Because the diatom flora of Baffin Island lakes is taxonomically similar to that in dilute lakes elsewhere in eastern North America, pH inferences were also made by WA calibration using the pH optima from the Paleoecological Investigation of Recent Lake Acidification (PIRLA; Camburn and Charles, 2000), and the Environmental Monitoring and Assessment Program (EMAP; Dixit et al., 1999). (3) The overall importance of pH as a predictor of diatom assemblage composition was evaluated by comparing transfer function results to sample scores on the first principal component extracted from the diatom relative frequencies. Principal components analysis (PCA) is an indirect ordination technique that models species abundances as linear responses along synthetic orthogonal axes (ter Braak, 1987). In contrast to WA inferences, PCA does not employ any a priori ecological characterization of diatom taxa with respect to pH or any other environmental variable. Although the two lakes are chemically similar, their diatom floras differ markedly. Before ca. 2500 yr B.P., the sediments of Kekerturnak Lake were dominated by the circumneutral taxa Cyclotella rossi, Brachysira vitrea, Aulacoseira lirata, and Stauroforma exiguiformis. Thereafter, these taxa were largely replaced by the more acidophilic A. GEOLOGY, March 2002 more complicated (Fig. 4); two intervals of increasing pH (5000–4000 yr B.P. and 3000– 2000 yr B.P.) are separated by periods of more acidic conditions, the latter of which (1800– 200 yr B.P.) was characterized by a pH of ;6.0. A rapid pH increase is registered in the uppermost samples. The robustness of these trends is verified by the PCA results (Fig. 4), which closely mimic WA pH inferences. Alkaliphilic diatoms (fragilarioid taxa) load positively on axis 1, whereas low species scores are typical of acidophils (Aulacoseira distans, A. perglabra, Eunotia spp.). The remarkable correspondence between the PCA and WA results indicates (1) that pH is the dominant environmental control over diatom assemblage composition, and (2) that WA pH inferences faithfully track past variability in this parameter. Figure 4. Diatom-inferred pH reconstructions from (A) Kekerturnak Lake and (B) Fog Lake over 5 k.y. Three curves at left are based on weighted average calibration, using Baffin Island training set (circles), and pH optima from Paleoecological Investigation of Recent Lake Acidification (PIRLA) and Environmental Monitoring and Assessment Program (EMAP) (gray lines). Arrows indicate measured pH; pH inferences are shown next to principal components analysis (PCA) first axis sample scores. At right are profiles of diatom concentrations. distans and C. stelligera. In Fog Lake, sediments deposited between 5000 and 2000 yr B.P. are characterized by S. exiguiformis and Staurosira construens var. venter, circumneutral and alkaliphilic taxa, respectively. The acidophils A. distans, Eunotia rhomboidea, E. vanheurkii, and Peronia fibula became conspicuous after 2000 yr B.P., until the upper 2 cm of the core, when S. exiguiformis rebounded, accompanied by increased frequencies of Nitzschia perminuta. Despite these ecological differences, diatom-inferred pH reconstructions from both lakes record a coherent pattern of decline throughout the late Holocene (Fig. 4). Although WA reconstructions using the PIRLA GEOLOGY, March 2002 and EMAP optima differ from those based on the Baffin Island training set, the directions and amplitudes of inferred pH change are parallel. Discrepancies between the inference models arise from sampling that alternately biased more acidic (PIRLA) and more alkaline (EMAP) lakes than those on Baffin Island. Close correspondence between measured pH and core-top reconstructions (Fig. 4) indicates, as expected, that the Baffin Island model provides the most accurate pH inferences. Diatominferred pH consistently exceeded 6.6 prior to 2500 yr B.P. in Kekerturnak Lake; peak values were ;6.8 between 4000 and 3000 yr B.P. After 2500 yr B.P., pH decreased to modern values (6.2–6.3). The record from Fog Lake is DISCUSSION AND CONCLUSIONS Several processes linking lake-water pH and climate are known (Sommaruga-Wögrath et al., 1997; Koinig et al., 1998). In lakes on eastern Baffin Island, edaphic contributions to alkalinity from base cations derived by weathering and eolian dust are unlikely to be as important as in other regions. In addition to the highly resistant character of local bedrock, lakes are icebound for more than 10 months of the year, effectively isolating them from external influences for all but a few weeks annually. For example, increased dust flux over Cumberland Peninsula during the late Holocene (Zdanowicz et al., 2000) did not attenuate lake acidification trends through enhanced atmospheric loading of base cations. Instead, it is argued that the coupling of climate and pH is regulated by within-lake processes, the most important of which involve dissolved inorganic carbon (DIC) speciation. Given low solute concentrations, lake-water pH, whether measured directly or remotely sensed by diatom assemblages, is regulated by the DIC system, which is in turn modulated by the duration of ice cover. Although CO2 supersaturation occurs in a variety of lake types worldwide (Cole et al., 1994), it is prevalent when ice precludes the evasion of respired CO2 to the atmosphere. For example, CO2 partial pressures in Alaskan lakes are 3–14 times greater under ice than during the openwater season (Kling et al., 1992). Furthermore, ice cover reduces light penetration and hence primary productivity, so that photosynthetic drawdown of dissolved CO2 is minimal. Because CO2 dominates the DIC pool under such conditions, pH declines accordingly, which is the situation envisaged for cold paleoclimatic intervals. Conversely, during warmer periods, longer ice-free seasons promote equilibration between dissolved and atmospheric CO2, eliminating supersaturation in 217 the water column. Enhanced algal production further reduces limnetic CO2, shifting DIC toward greater proportions of HCO3–, and driving pH increases. When applied to the Baffin Island lakes, this model predicts a reduction of algal productivity in concert with Neoglacial cooling, which is supported by progressive decreases in diatom concentrations (and fluxes) in both lakes (Fig. 4). The late Holocene pH trends from Kekerturnak and Fog Lakes are not monotonic. Both lakes record increased diatom-inferred pH between ca. 3500 and 2500 yr B.P., followed by marked acidification. The latter may reflect limnological responses to cooling associated with enhanced Arctic Ocean outflow into Baffin Bay (Dyke et al., 1996). Both lakes reached their pH minima after 2000 yr B.P., in agreement with independent records of cold prevailing conditions (Fig. 1). The rapid increase in pH observed in the post–Little Ice Age sediments of Fog Lake is not captured in Kekerturnak, although both lakes register increases in diatom concentrations during this interval. It remains to be shown how directly these observations relate to recent warming of the Arctic (Overpeck et al., 1997). The sensitivity of lake-water pH to temperature can only be estimated at present. If the amplitude of Neoglacial summer cooling at the latitude of the study sites is estimated as 3.0 8C (Andrews et al., 1981; Dahl-Jensen et al., 1998), then pH appears to be coupled to air temperature on the order of 0.2 units per degree Celsius. From the diatom-inferred pH results, late Holocene cooling therefore appears to have been punctuated by several events of 1–2 8C amplitude. Although additional records are needed to fully test this possibility, it is consistent with suggestions of pronounced Holocene climate variability in the North Atlantic sector (Bond et al., 1997). Although climate warming may raise the pH of Baffin Island lakes by prolonging the icefree season, this relationship is fully dependent upon the unbuffered character of these lakes, which allows the direct control of pH by DIC dynamics. This same condition enhances the vulnerability of these lakes to atmospheric inputs of strong-acid anions of anthropogenic origin, implying that the relationship between climate and pH may easily be disrupted. ACKNOWLEDGMENTS This research was funded by the National Science Foundation (ATM-9402657). The support of the Nunavut Research Institute and the hamlet of Qikiqtarjuaq is gratefully acknowledged. I thank 218 Gifford Miller and Ernest Joynt for data and ideas and the reviewers for improving clarity and content. 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