On the interpretation of recharge estimates from steady-state model calibrations

Ground water recharge is often estimated through the calibration of ground water flow models. We examine the nature of calibration errors by considering some simple mathematical and numerical calculations. From these calculations, we conclude that calibrating a steady-state ground water flow model to water level extremes yields estimates of recharge that have the same value as the time-varying recharge at the time the water levels are measured. These recharge values, however, are a subdued version of the actual transient recharge signal. In addition, calibrating a steady-state ground water flow model to data collected during periods of rising water levels will produce recharge values that underestimate the actual transient recharge. Similarly, calibrating during periods of falling water levels will overestimate the actual transient recharge. We also demonstrate that average water levels can be used to estimate the actual average recharge rate provided that water level data have been collected for a sufficient amount of time.     

Michigan basin regional ground water flow discharge to three Great Lakes

Ground water discharge to the Great Lakes around the Lower Peninsula of Michigan is primarily from recharge in riparian basins and proximal upland areas that are especially important to the northern half of the Lake Michigan shoreline. A steady-state finite-difference model was developed to simulate ground water flow in four regional aquifers in Michigan's Lower Peninsula: the Glaciofluvial, Saginaw, Parma-Bayport, and Marshall aquifers interlayered with the Till/"red beds," Saginaw, and Michigan confining units, respectively. The model domain was laterally bound by a continuous specified-head boundary, formed from lakes Michigan, Huron, St. Clair, and Erie, with the St. Clair and Detroit River connecting channels. The model was developed to quantify regional ground water flow in the aquifer systems using independently determined recharge estimates. According to the flow model, local stream stages and discharges account for 95% of the overall model water budget; only 50% enters the lakes directly from the ground water system. Direct ground water discharge to the Great Lakes' shorelines was calculated at 36 m3/sec, accounting for 5% of the overall model water budget. Lowland areas contribute far less ground water discharge to the Great Lakes than upland areas. The model indicates that Saginaw Bay receives only approximately 1.13 m3/sec ground water; the southern half of the Lake Michigan shoreline receives only approximately 2.83 m3/sec. In contrast, the northern half of the Lake Michigan shoreline receives more than 17 m3/sec from upland areas.     

Geochemical quantification of semiarid mountain recharge

Analysis of a typical semiarid mountain system recharge (MSR) setting demonstrates that geochemical tracers help resolve the location, rate, and seasonality of recharge as well as ground water flowpaths and residence times. MSR is defined as the recharge at the mountain front that dominates many semiarid basins plus the often-overlooked recharge through the mountain block that may be a significant ground water resource; thus, geochemical measurements that integrate signals from all flowpaths are advantageous. Ground water fluxes determined from carbon-14 ((14)C) age gradients imply MSR rates between 2 x 10(6) and 9 x 10(6) m(3)/year in the Upper San Pedro Basin, Arizona, USA. This estimated range is within an order of magnitude of, but lower than, prior independent estimates. Stable isotopic signatures indicate that MSR has a 65% +/- 25% contribution from winter precipitation and a 35% +/- 25% contribution from summer precipitation. Chloride and stable isotope results confirm that transpiration is the dominant component of evapotranspiration (ET) in the basin with typical loss of more than 90% of precipitation-less runoff to ET. Such geochemical constraints can be used to further refine hydrogeologic models in similar high-elevation relief basins and can provide practical first estimates of MSR rates for basins lacking extensive prior hydrogeologic measurements.     

Forensic isotope analysis to refine a hydrologic conceptual model

Water resources in the arid southwestern United States are frequently the subject of conflict from competing private and public interests. Legal remedies may remove impasses, but the technical analysis of the problem often determines the future success of legal solutions. In Owens Valley, California, the source of water for the Los Angeles Aqueduct (LAA) is flow diverted from the Owens River and its tributaries and ground water from valley aquifers. Future management of ground water delivered to the LAA needs technical support regarding quantity available, interconnection of shallow and confined aquifers, impact on local springs, and rate of recharge. Ground water flow models and ground water composition are tools already in use, but these have large uncertainty for local interpretations. This study conducted targeted sampling of springs and wells to evaluate the hydrologic system to corroborate conceptual and numerical models. The effort included measurement of intrinsic isotopic composition at key locations in the aquifers. The stable isotopic data of boron (delta(11)B), sulfur (delta(34)S), oxygen (delta(18)O), hydrogen (delta D), and tritium ((3)H) supported by basic chemical data provided rules for characterizing the upper and the lower aquifer system, confirmed the interpretation of ground water flow near faults and flow barriers, and detected hydraulic connections between the LAA and the perennial springs at key locations along the unlined reach of the LAA. This study exemplifies the use of forensic isotopic approaches as independent checks on the consistency of interpretations of conceptual models of a ground water system and the numerical hydrologic simulations.     

Ground water recharge and flow characterization using multiple isotopes

Stable isotopes of delta(18)O, delta(2)H, and (13)C, radiogenic isotopes of (14)C and (3)H, and ground water chemical compositions were used to distinguish ground water, recharge areas, and possible recharge processes in an arid zone, fault-bounded alluvial aquifer. Recharge mainly occurs through exposed stream channel beds as opposed to subsurface inflow along mountain fronts. This recharge distribution pattern may also occur in other fault-bounded aquifers, with important implications for conceptualization of ground water flow systems, development of ground water models, and ground water resource management. Ground water along the mountain front near the basin margins contains low delta(18)O, (14)C (percent modern carbon [pmC]), and (3)H (tritium units [TU]), suggesting older recharge. In addition, water levels lie at greater depths, and basin-bounding faults that locally act as a flow barrier may further reduce subsurface inflow into the aquifer along the mountain front. Chemical differences in ground water composition, attributed to varying aquifer mineralogy and recharge processes, further discriminate the basin-margin and the basin-center water. Direct recharge through the indurated sandstones and mudstones in the basin center is minimal. Modern recharge in the aquifer is mainly through the broad, exposed stream channel beds containing coarse sand and gravel where ground water contains higher delta(18)O, (14)C (pmC), and (3)H (TU). Spatial differences in delta(18)O, (14)C (pmC), and (3)H (TU) and occurrences of extensive mudstones in the basin center suggest sluggish ground water movement, including local compartmentalization of the flow system.     

Distinguishing sources of ground water recharge by using delta2H and delta18O

Stable isotope values of hydrogen and oxygen from precipitation and ground water samples were compared by using a volumetrically based mixing equation and stable isotope gradient to estimate the season and location of recharge in four basins. Stable isotopes were sampled at 11 precipitation sites of differing elevation during a 2-year period to quantify seasonal stable isotope contributions as a function of elevation. Supplemental stable isotope data collected by the International Atomic Energy Association during a 14-year period were used to reduce annual variability of the mean seasonal stable isotope data. The stable isotope elevation relationships and local precipitation elevation relationships were combined by using a digital elevation model to calculate the total volumetric contribution of water and stable isotope values as a function of elevation within the basins. The results of these precipitation calculations were compared to measured ground water stable isotope values at the major discharge points near the terminus of the basins. Volumetric precipitation contributions to recharge were adjusted to isolate contributing elevations. This procedure provides an improved representation of recharge contributions within the basins over conventional stable isotope methods. Stable isotope values from wells and springs at the terminus of each basin were used to infer the elevations of precipitation important for recharge of the regional ground water flow system. Ancillary climatic, geologic, and stable isotope values were used to further constrain the location where precipitation is entering the ground water flow system.     

Mass transport triggered by heavy rainfall: the role of endorheic basins and epikarst in a regional karst aquifer

This study aims at recognizing the mechanisms of mass transport between the karst surface and the saturated zone in a morphostructural relief of the Mesozoic karst carbonate platform of Murgia (Puglia, Southern Italy). The large dimension of the karst aquifer, the regional scale of the flow system, the boundary condition constituted by the sea, and the lack of freshwater springs constrain to the use of wells as monitoring points and limit the study area to the recharge area comprising 986 endorheic basins. The concentrations of non‐reactive tracers (nitrates) in the waters of autogenic recharge (from endorheic basins) have been modeled through the evaluation of effective infiltration, land use, and nitrogen surplus, with reference to a time window, which includes a low precipitation period followed by significant rainfall events. The comparison between the modeled nitrate concentrations and the nitrate concentrations measured in ground waters, coupled with the analysis of groundwater chemograms and records of hydraulic heads (all referred to the same time window), allows inferring the mechanism of mass transport between the karst surface and the groundwater table. The mass transport conceptual model requires the presence of the epikarst. The infiltration of significant rainfall in the endorheic basins after a low precipitation period displaces waters stored in the epikarst toward the saturated zone. Ground waters in the post‐event period show higher concentrations of nitrates, lower concentrations of total organic carbon, and higher Mg/Ca ratios than both those of the pre‐event period and the autumn‐winter recharge period. The post‐event recharge from epikarst storage determines a transient hazard of groundwater pollution with a time lag from the occurrence of the heavy rainfall.     

Ground water flow analysis of a mid-Atlantic outer coastal plain watershed, Virginia, U.S.A

Models for ground water flow (MODFLOW) and particle tracking (MODPATH) were used to determine ground water flow patterns, principal ground water discharge and recharge zones, and estimates of ground water travel times in an unconfined ground water system of an outer coastal plain watershed on the Delmarva Peninsula, Virginia. By coupling recharge and discharge zones within the watershed, flowpath analysis can provide a method to locate and implement specific management strategies within a watershed to reduce ground water nitrogen loading to surface water. A monitoring well network was installed in Eyreville Creek watershed, a first-order creek, to determine hydraulic conductivities and spatial and temporal variations in hydraulic heads for use in model calibration. Ground water flow patterns indicated the convergence of flow along the four surface water features of the watershed; primary discharge areas were in the nontidal portions of the watershed. Ground water recharge zones corresponded to the surface water features with minimal development of a regional ground water system. Predicted ground water velocities varied between < 0.01 to 0.24 m/day, with elevated values associated with discharge areas and areas of convergence along surface water features. Some ground water residence times exceeded 100 years, although average residence times ranged between 16 and 21 years; approximately 95% of the ground water resource would reflect land use activities within the last 50 years.     

Modeling a Ground Water Circulation Well Alternative

Ground water circulation wells (GCWs) provide an appealing alternative to typical pump-and-treat ground water remediation systems because of the inherent resource-conservative nature of the GCW systems. GCW performance prediction is challenging because the consideration of extraction and recharge in a single well is unusual for most practitioners, the technology is relatively new, and a meaningful body of literature has not been published. A three-part evaluation process using state-of-the-practice numerical ground water flow and mass transport models was developed for application during GCW pilot studies at the former Nebraska Ordnance Plant site. A small-scale ground water flow model was developed during the pilot study planning process to predict the system performance and to locate performance-measuring monitoring wells. Key predictions included the capture zone predicted to develop upgradient of the GCW, the downgradierit GCW recharge zone, and the circulation zone centered on the GCW. The flow model was subsequently verified using ground water elevation data and contaminant concentration data collected during pilot study operation. Aquifer parameters were reestimated as a result of the verification process. Those parameter values were used as input to a larger scale model, which was used to develop a remedial alternative consisting of multiple GCW systems.     

Distinguishing Mountain Front and Mountain Block Recharge in an Intermontane Basin of the Himalayan Region

Intermontane basin aquifers worldwide, particularly in the Himalayan region, are recharged largely by the adjoining mountains. Recharge in these basins can occur either by water infiltrating from streams near mountain fronts (MFs) as mountain front recharge (MFR) or by sub-surface mountain block infiltration as mountain block recharge (MBR). MFR and MBR recharge are challenging to distinguish and are least quantified, considering the lack of extensive understanding of the hydrological processes in the mountains. This study used oxygen and hydrogen isotopes (δ¹⁸O and δ²H), electrical conductivity (EC) data, hydraulic head, and groundwater level data to differentiate MFR and MBR. Groundwater level data provide information about the groundwater-surface water interactions and groundwater flow directions, whereas isotopes and EC data are used to distinguish and quantify different recharge sources. The present methodology is tested in an intermontane basin of the Himalayan region. The results suggest that karst springs (KS) and deep groundwater (DGW) recharge are dominated by snowmelt (47% ± 10% and 46% ± 9%) as MBR from adjacent mountains, insignificantly affected by evaporation. The hydraulic head data and isotopes indicate Quaternary shallow groundwater (SGW) aquifer system recharge as MFR of local meteoric water with significant evaporation. The results indicate several flow paths in the aquifer system, a local flow for KS, intermediate flow for SGW, and regional flow for DGW. The findings will significantly impact water resource management in the area and provide vital baseline knowledge for sustainable groundwater management in other Himalayan intermontane basins.     

Delineation of regional arid karstic aquifers: an integrative data approach

This research integrates data procedures for the delineation of regional ground water flow systems in arid karstic basins with sparse hydrogeologic data using surface topography data, geologic mapping, permeability data, chloride concentrations of ground water and precipitation, and measured discharge data. This integrative data analysis framework can be applied to evaluate arid karstic aquifer systems globally. The accurate delineation of ground water recharge areas in developing aquifer systems with sparse hydrogeologic data is essential for their effective long-term development and management. We illustrate the use of this approach in the Cuatrociénegas Basin (CCB) of Mexico. Aquifers are characterized using geographic information systems for ground water catchment delineation, an analytical model for interbasin flow evaluation, a chloride balance approach for recharge estimation, and a water budget for mapping contributing catchments over a large region. The test study area includes the CCB of Coahuila, Mexico, a UNESCO World Biosphere Reserve containing more than 500 springs that support ground water-dependent ecosystems with more than 70 endemic organisms and irrigated agriculture. We define recharge areas that contribute local and regional ground water discharge to springs and the regional flow system. Results show that the regional aquifer system follows a topographic gradient that during past pluvial periods may have linked the Río Nazas and the Río Aguanaval of the Sierra Madre Occidental to the Río Grande via the CCB and other large, currently dry, upgradient lakes.     

Catchment-Wide Groundwater Budget for the Inkomati-Usuthu Water Management Area in South Africa

In South Africa, approximately 98% of the predicted total surface water resources are already being used up. Consequently, the National Water Resource Strategy considers groundwater to be important for the future planning and management of water resources. In this case, quantifying groundwater budgets is a prerequisite because they provide a means for evaluating the availability and sustainability of a water supply. This study estimated the regional groundwater budgets for the Inkomati-Usuthu Water Management Area (Usuthu, Komati, Sabie-Sand, and Crocodile) using the classical hydrological continuity equation. The equation was used to describe prevailing feedback loops between groundwater draft, recharge, baseflow, and storage change. The results were coarser scale estimates which, beforehand, were derived from the 2006 study. In the years to follow, groundwater reliance intensified and there was also the historic 2015/2016 drought. This inevitably led to an increased draft while the rest of the components of the groundwater budgets experienced decreases. Both Crocodile and Sabie-Sand experienced groundwater storage depletion which led to reduced baseflow and groundwater availability, while groundwater recharge contrarily increased due to capture. Conversely, the other two catchments experienced relatively lower drafts with correspondingly higher groundwater availability and recharge while storage change was positive. The results highlighted the need for adaptive water management whose effectiveness relies on predictive studies. Consequently, future models should be developed to capture the spatial and temporal dynamism of the natural groundwater budget due to climate change, water demands, and population growth predictions.     

Spatial and temporal variability of ground water recharge in central Australia: a tracer approach

Two environmental tracer methods are applied to the Ti-Tree Basin in central Australia to shed light on the importance of recharge from floodouts of ephemeral rivers in this arid environment. Ground water carbon-14 concentrations from boreholes are used to estimate the average recharge rate over the interval between where the ground water sample first entered the saturated zone and the bore. Environmental chloride concentrations in ground water samples provide estimates of the recharge rate at the exact point in the landscape where the sample entered the saturated zone. The results of the two tracer approaches indicate that recharge rates around one of the rivers and an extensive floodplain are generally higher than rates of diffuse recharge that occurs in areas of lower topographic relief. Ground water 2H/1H and 18O/16O compositions are all depleted in the heavier isotopes (delta2H = -67 per thousand to -50 per thousand; delta18O = -9.2 per thousand to -5.7%o) compared with the long-term, amount-weighted mean isotopic composition of rainfall in the area (delta2H = -33.8 per thousand; delta18O = -6.3 per thousand). This indicates that recharge throughout the basin occurs only after intense rainfall events of at least 150 to 200 mm/month. Finally, a recharge map is developed to highlight the spatial extent of the two recharge mechanisms. Floodout recharge to the freshest ground water (TDS <1,000 mg/L) is approximately 1.9 mm/year compared with a mean recharge rate of approximately 0.2 mm/year to the remainder of the basin. These findings have important implications for management of the ground water resource.     

The Water Budget Myth and Its Recharge Controversy: Linear vs. Nonlinear Models

The water budget myth, which is the idea that safe pumping must not exceed the initial recharge, gave rise to a controversy about the role of recharge in assessing the sustainability of groundwater development. To refute the concept of safe yield, a simplified water budget equation is used, which equals the total pumping rate to the sum of capture and storage change. Since initial recharge and discharge are canceled out from this equation, it is concluded that sustainable pumping has nothing to do with recharge. Investigating the assumptions underlying this equation, it is seen that it expresses the superposition principle, which implicitly assumes the groundwater reservoir can be depleted indefinitely and boundary conditions are an infinite source of water. To evaluate sustainability, however, the limits of the aquifer system must be examined accurately. Theoretically, this can only be accomplished applying nonlinear models, in which case setting up the simplified water budget equation is impossible without knowing the initial conditions. Hence, excluding recharge when assessing sustainable pumping may not be done inconsiderately, which is illustrated by two examples. An analytical solution, developed by Ernst in 1971 to simulate flow to a well in a polder area with a nonlinear function for drainage, even shows that it is not necessarily a misconception to assume the cone of depression stops expanding when the pumping rate is balanced by the infiltration rate.     

Land Water Storage Changes from Ground and Space Geodesy: First Results from the GHYRAF (Gravity and Hydrology in Africa) Experiment

This paper is devoted to the first results from the GHYRAF (Gravity and Hydrology in Africa) experiment conducted since 2008 in West Africa and is aimed at investigating the changes in water storage in different regions sampling a strong rainfall gradient from the Sahara to the monsoon zone. The analysis of GPS vertical displacement in Niamey (Niger) and Djougou (Benin) shows that there is a clear annual signature of the hydrological load in agreement with global hydrology models like GLDAS. The comparison of GRACE solutions in West Africa, and more specifically in the Niger and Lake Chad basins, reveals a good agreement for the large scale annual water storage changes between global hydrology models and space gravity observations. Ground gravity observations done with an FG5 absolute gravimeter also show signals which can be well related to measured changes in soil and ground water. We present the first results for two sites in the Sahelian band (Wankama and Diffa in Niger) and one (Djougou in Benin) in the Sudanian monsoon region related to the recharge–discharge processes due to the monsoonal event in summer 2008 and the following dry season. It is confirmed that ground gravimetry is a useful tool to constrain local water storage changes when associated to hydrological and subsurface geophysical in situ measurements.     

Geochemical imaging of flow near an artificial recharge facility, Orange County, California

Critical for the management of artificial recharge operations is detailed knowledge of ground water dynamics near spreading areas. Geochemical tracer techniques including stable isotopes of water, tritium/helium-3 (T/3He) dating, and deliberate gas tracer experiments are ideally suited for these investigations. These tracers were used to evaluate flow near an artificial recharge site in northern Orange County, California, where approximately 2.5 x 10(8) m3 (200,000 acre-feet) of water are recharged annually. T/3He ages show that most of the relatively shallow ground water within 3 km of the recharge facilities have apparent ages < 2 years; further downgradient apparent ages increase, reaching > 20 years at approximately 6 km. Gas tracer experiments using sulfur hexafluoride and xenon isotopes were conducted from the Santa Ana River and two spreading basins. These tracers were followed in the ground water for more than two years, allowing subsurface flow patterns and flow times to be quantified. Results demonstrate that mean horizontal ground water velocities range from < 1 to > 4 km/year. The leading edges of the tracer patch moved at velocities about twice as fast as the center of mass. Leading edge velocities are important when considering the potential transport of microbes and other "time sensitive" contaminants and cannot be determined easily with other methods. T/3He apparent ages and tracer travel times agreed within the analytical uncertainty at 16 of 19 narrow screened monitoring wells. By combining these techniques, ground water flow was imaged with time scales on the order of weeks to decades.     

Isotope methods for management of shared aquifers in northern Africa

Access to fresh water is one of the major issues of northern and sub-Saharan Africa. The majority of the fresh water used for drinking and irrigation is obtained from large ground water basins where there is minor contemporary recharge and the aquifers cross national borders. These aquifers include the Nubian Aquifer System shared by Chad, Egypt, Libya, and Sudan; the Iullemeden Aquifer System, extending over Niger, Nigeria, Mali, Benin, and Algeria; and the Northwest Sahara Aquifer System shared by Algeria, Libya, and Tunisia. These resources are subject to increased exploitation and may be severely stressed if not managed properly as witnessed already by declining water levels. In order to make appropriate decisions for the sustainable management of these shared water resources, planners and managers in different countries need an improved knowledge base of hydrological information. Three technical cooperation projects related to aquifer systems will be implemented by the International Atomic Energy Agency, in collaboration with the United Nations Educational, Scientific and Cultural Organization and United Nations Development Programme/Global Environmental Facility. These projects focus on isotope hydrology studies to better quantify ground water recharge and dynamics. The multiple isotope approach combining commonly used isotopes 18O and 2H together with more recently developed techniques (chlorofluorocarbons, 36Cl, noble gases) will be applied to improve the conceptual model to study stratification and ground water flows. Moreover, the isotopes will be an important indicator of changes in the aquifer due to water abstraction, and therefore they will assist in the effort to establish a sustainable ground water management.     

Modeled Ground Water Age Distributions

The age of ground water in any given sample is a distributed quantity representing distributed provenance (in space and time) of the water. Conventional analysis of tracers such as unstable isotopes or anthropogenic chemical species gives discrete or binary measures of the presence of water of a given age. Modeled ground water age distributions provide a continuous measure of contributions from different recharge sources to aquifers. A numerical solution of the ground water age equation of Ginn (1999) was tested both on a hypothetical simplified one‐dimensional flow system and under real world conditions. Results from these simulations yield the first continuous distributions of ground water age using this model. Complete age distributions as a function of one and two space dimensions were obtained from both numerical experiments. Simulations in the test problem produced mean ages that were consistent with the expected value at the end of the model domain for all dispersivity values tested, although the mean ages for the two highest dispersivity values deviated slightly from the expected value. Mean ages in the dispersionless case also were consistent with the expected mean ages throughout the physical model domain. Simulations under real world conditions for three dispersivity values resulted in decreasing mean age with increasing dispersivity. This likely is a consequence of an edge effect. However, simulations for all three dispersivity values tested were mass balanced and stable demonstrating that the solution of the ground water age equation can provide estimates of water mass density distributions over age under real world conditions.     

An assessment of aquifer storage recovery using ground water flow models

Owing to increased demands on ground water accompanied by increased drawdowns, technologies that use recharge options, such as aquifer storage recovery (ASR), are being used to optimize available water resources and reduce adverse effects of pumping. In this paper, three representative ground water flow models were created to assess the impact of hydrogeologic and operational parameters/factors on recovery efficiency of ASR systems. Flow/particle tracking and solute transport models were used to track the movement of water during injection, storage, and recovery. Results from particle tracking models consistently produced higher recovery efficiency than the solute transport models for the parameters/properties examined because the particle tracking models neglected mixing of the injected and ambient water. Mixing between injected and ambient water affected recovery efficiency. Results from this study demonstrate the interactions between hydrogeologic and operational parameters on predictions of recovery efficiency. These interactions are best simulated using coupled numerical ground water flow and transport models that include the effects of mixing of injected water and ambient ground water.     

Characterization of lake water and ground water movement in the littoral zone of Williams Lake,a closed‐basin lake in north central Minnesota

Williams Lake, Minnesota is a closed‐basin lake that is a flow‐through system with respect to ground water. Ground‐water input represents half of the annual water input and most of the chemical input to the lake. Chemical budgets indicate that the lake is a sink for calcium, yet surficial sediments contain little calcium carbonate. Sediment pore‐water samplers (peepers) were used to characterize solute fluxes at the lake‐water–ground‐water interface in the littoral zone and resolve the apparent disparity between the chemical budget and sediment data. Pore‐water depth profiles of the stable isotopes δ¹⁸O and δ²H were non‐linear where ground water seeped into the lake, with a sharp transition from lake‐water values to ground‐water values in the top 10 cm of sediment. These data indicate that advective inflow to the lake is the primary mechanism for solute flux from ground water. Linear interstitial velocities determined from δ²H profiles (316 to 528 cm/yr) were consistent with velocities determined independently from water budget data and sediment porosity (366 cm/yr). Stable isotope profiles were generally linear where water flowed out of the lake into ground water. However, calcium profiles were not linear in the same area and varied in response to input of calcium carbonate from the littoral zone and subsequent dissolution. The comparison of pore‐water calcium profiles to pore‐water stable isotope profiles indicate calcium is not conservative. Based on the previous understanding that 40–50 % of the calcium in Williams Lake is retained, the pore‐water profiles indicate aquatic plants in the littoral zone are recycling the retained portion of calcium. The difference between the pore‐water depth profiles of calcium and δ¹⁸O and δ²H demonstrate the importance of using stable isotopes to evaluate flow direction and source through the lake‐water–ground‐water interface and evaluate mechanisms controlling the chemical balance of lakes. Published in 2003 by John Wiley & Sons, Ltd.