Nutrient Removal during Stormwater Aquifer Storage and Recovery in an Anoxic Carbonate Aquifer.

Stormwater harvesting coupled to managed aquifer recharge (MAR) provides a means to use the often wasted stormwater resource while also providing protection of the natural and built environment. Aquifers can act as a treatment barrier within a multiple-barrier approach to harvest and use urban stormwater. However, it remains challenging to assess the treatment performance of a MAR scheme due to the heterogeneity of aquifers and MAR operations, which in turn influences water treatment processes. This study uses a probabilistic method to evaluate aquifer treatment performance based on the removal of total organic C (TOC), N, and P during MAR with urban stormwater in an anoxic carbonate aquifer. Total organic C, N, and P are represented as stochastic variables and described by probability density functions (PDFs) for the "injectant" and "recovery"; these injectant and recovery PDFs are used to derive a theoretical MAR removal efficiency PDF. Four long-term MAR sites targeting one of two tertiary carbonate aquifers (T1 and T2) were used to describe the nutrient removal efficiencies. Removal of TOC and total N (TN) was dominated by redox processes, with median removal of TOC between 50 and 60% at all sites and TN from 40 to 50% at three sites with no change at the fourth. Total P removal due to filtration and sorption accounted for median removal of 29 to 53%. Thus, the statistical method was able to characterize the capacity of the anoxic carbonate aquifer treatment barrier for nutrient removal, which highlights that aquifers can be an effective long-term natural treatment option for management of water quality, as well as storage of urban stormwater.

Temperature Dependence of Photodegradation of Dissolved Organic Matter to Dissolved Inorganic Carbon and Particulate Organic Carbon.

Photochemical transformation of dissolved organic matter (DOM) has been studied for more than two decades. Usually, laboratory or "in-situ" experiments are used to determine photodegradation variables. A common problem with these experiments is that the photodegradation experiments are done at higher than ambient temperature. Five laboratory experiments were done to determine the effect of temperature on photochemical degradation of DOM. Experimental results showed strong dependence of photodegradation on temperature. Mathematical modeling of processes revealed that two different pathways engaged in photochemical transformation of DOM to dissolved inorganic carbon (DIC) strongly depend on temperature. Direct oxidation of DOM to DIC dominated at low temperatures while conversion of DOM to intermediate particulate organic carbon (POC) prior to oxidation to DIC dominated at high temperatures. It is necessary to consider this strong dependence when the results of laboratory experiments are interpreted in regard to natural processes. Photodegradation experiments done at higher than ambient temperature will necessitate correction of rate constants.

Forecasting cyanobacteria dominance in Canadian temperate lakes.

Predictive models based on broad scale, spatial surveys typically identify nutrients and climate as the most important predictors of cyanobacteria abundance; however these models generally have low predictive power because at smaller geographic scales numerous other factors may be equally or more important. At the lake level, for example, the ability to forecast cyanobacteria dominance is of tremendous value to lake managers as they can use such models to communicate exposure risks associated with recreational and drinking water use, and possible exposure to algal toxins, in advance of bloom occurrence. We used detailed algal, limnological and meteorological data from two temperate lakes in south-central Ontario, Canada to determine the factors that are closely linked to cyanobacteria dominance, and to develop easy to use models to forecast cyanobacteria biovolume. For Brandy Lake (BL), the strongest and most parsimonious model for forecasting % cyanobacteria biovolume (% CB) included water column stability, hypolimnetic TP, and % cyanobacteria biovolume two weeks prior. For Three Mile Lake (TML), the best model for forecasting % CB included water column stability, hypolimnetic TP concentration, and 7-d mean wind speed. The models for forecasting % CB in BL and TML are fundamentally different in their lag periods (BL = lag 1 model and TML = lag 2 model) and in some predictor variables despite the close proximity of the study lakes. We speculate that three main factors (nutrient concentrations, water transparency and lake morphometry) may have contributed to differences in the models developed, and may account for variation observed in models derived from large spatial surveys. Our results illustrate that while forecast models can be developed to determine when cyanobacteria will dominate within two temperate lakes, the models require detailed, lake-specific calibration to be effective as risk-management tools.

Interaction of extrinsic chemical factors affecting photodegradation of dissolved organic matter in aquatic ecosystems.

Photochemical degradation of dissolved organic matter (DOM) plays an important role in the carbon cycle. Irradiation experiments were conducted to evaluate the influence of chemical factors, specifically those expected to be altered in natural waters by atmospheric acid deposition, on photodegradation of DOM. These included pH, nitrate, iron and calcium. The experiments were carried out using stream and lake water samples with a wide range of dissolved organic carbon (DOC) concentration. Decreasing DOC concentration along with decreasing absorbance was observed during three-week exposures to natural solar radiation as well as during laboratory experiments with artificial solar radiation. The pH of the samples significantly affected degradation rates of DOM especially with elevated iron, while no influence of nitrate or calcium concentration was observed. Addition of Fe(III) did not significantly affect photodegradation and photobleaching rate constants in samples at circumneutral pH. Acid pH increased photodegradation rates. The results suggest that photodegradation rates of DOM will decrease during recovery from acidification. Hence, lower photodegradation rates may be responsible for increases in DOM observed in some regions of North America and Europe.

Recovery of injected freshwater from a brackish aquifer with a multiwell system.

Herein we propose a multiple injection and recovery well system strategically operated for freshwater storage in a brackish aquifer. With the system we call aquifer storage transfer and recovery (ASTR) by using four injection and two production wells, we are capable of achieving both high recovery efficiency of injected freshwater and attenuation of contaminants through adequately long residence times and travel distances within the aquifer. The usual aquifer storage and recovery (ASR) scheme, in which a single well is used for injection and recovery, does not warrant consistent treatment of injected water due to the shorter minimum residence times and travel distances. We tested the design and operation of the system over 3 years in a layered heterogeneous limestone aquifer in Salisbury, South Australia. We demonstrate how a combination of detailed aquifer characterization and solute transport modeling can be used to maintain acceptable salinity of recovered water for its intended use along with natural treatment of recharge water. ASTR can be used to reduce treatment costs and take advantage of aquifers with impaired water quality that might locally not be otherwise beneficially used.

Application of a probabilistic modelling approach for evaluation of nitrogen, phosphorus and organic carbon removal efficiency during four successive cycles of aquifer storage and recovery (ASR) in an anoxic carbonate aquifer.

Aquifer storage is increasingly being recognised in its role as a treatment process barrier within a multiple barrier approach to water reuse. Aquifers are postulated to have the ability to provide sustainable treatment for removal of nitrogen, phosphorus and organic carbon, the dominant nutrient hazards in water recycling, but, to date this treatment performance has remained difficult to validate in field studies. This study applied a statistical method, proposed for validation of the performance of advanced water treatment processes, to evaluate nutrient removal during aquifer storage and recovery (ASR) with recycled water. Analysis of observed water quality changes during four successive ASR cycles with highly variable source water quality was used to describe the removal efficiencies for selected nutrients by an anoxic carbonate aquifer. The use of this method was found to be suitable to calculate removal efficiencies for total organic carbon (TOC) and total nitrogen (TN) over four ASR cycles with temporally variable concentrations of nutrients in the tertiary treated wastewater injectant. TOC and TN removal was dominated by redox processes, aerobic respiration and denitrification. Median removal of TOC ranged from 25 to 40% and TN from 46 to 87% over the four cycles. There was no observable reduction in this removal with time, suggesting that removal of TOC and TN by redox processes can be sustained in an ASR system. Contrastingly, total phosphorous (TP) was subject to reversible removal via adsorption and desorption processes and as a result, removal efficiency could not be calculated with this method. Thus in general, results indicated that this statistical method could be used to characterise the capacity of the anoxic carbonate aquifer treatment barrier for removal of carbon and nitrogen, but not for removal of phosphorus.

Temporal and spatial variation in Hg accumulation in zebra mussels (Dreissena polymorpha): possible influences of DOC and diet.

Zebra mussels (Dreissena polymorpha) are filter feeders located near the base of the foodweb and these animals are able to utilize a variety of carbon sources that may also vary seasonally. We conducted both a spatial and a temporal study in order to test the hypotheses: (1) dissolved organic carbon (DOC) concentrations influence Hg accumulation in zebra mussels sampled from a series of lakes and (2) seasonal variations in diet influence Hg accumulation. In the spatial study, we found a significant negative relationship between Hg concentrations and DOC concentrations, suggesting an influence of DOC on Hg bioaccumulation. In the temporal study, we used stable isotope ratios of nitrogen (δ(15)N) and carbon (δ(13)C) as ecological tools to provide a temporally integrated description of the feeding ecology of zebra mussels. Both δ(15)N and δ(13)C varied seasonally in a similar manner: more depleted values occurred in the summer and more enriched values occurred in the fall. Mercury concentrations also varied significantly over the year, with highest concentrations occurring in the summer, followed by a progressive decrease in concentrations into the fall. The C/N ratio of zebra mussels also varied significantly over the year with the lowest values occurring mid-summer and then values increased in the fall and winter, suggesting that there was significant variation in lipid stores. These results indicate that in addition to any effect of seasonal dietary changes, seasonal variation in energy stores also appeared to be related to Hg levels in the zebra mussels. Collectively results from this study suggest that DOC concentrations, seasonal variation in diet and seasonal depletion of energy stores are all important variables to consider when understanding Hg accumulation in zebra mussels.

The impacts of ontogenetic dietary shifts in yellow perch (Perca flavescens) on Zn and Hg accumulation.

Yellow perch (Perca flavescens) undergo several ontogenetic dietary shifts, and consequently these fish feed at different trophic levels and rely on different carbon sources over their lifetime. Stable isotope ratios of nitrogen (δ(15)N) and carbon (δ(13)C) are powerful ecological tools that are used to provide a temporally integrated description of the feeding ecology of aquatic animals such as fish. The main objective of this study was to use stable isotopes of nitrogen and carbon to determine if dietary changes affected mercury (Hg) and zinc (Zn) accumulation in yellow perch ranging in size from approximately 5 cm to 27 cm. Results showed that Hg bioaccumulation generally increased with increasing trophic level in fish feeding at higher trophic levels, however, the relationship between Hg levels and δ(15)N was non-linear showing no relationship in small fish (less than 15 cm). In contrast, there was a negative, linear relationship between δ(15)N and Zn, suggesting that as perch fed at progressively higher trophic levels, less of Zn bioaccumulated. No relationship was observed between δ(13)C and metal levels in perch. Collectively, these results demonstrate a contrast in the behavior of Zn and Hg bioaccumulation in yellow perch as a function of trophic status.

Evaluating long-term trends in littoral benthic macroinvertebrate communities of lakes recovering from acid deposition.

The Mann-Kendall test has been proposed as a nonparametric method to evaluate trends in long-term water quality datasets with missing values, serial correlation, and non-normality. However, this test has rarely been used to evaluate long-term trends in biological data. In this study, we used the Mann-Kendall test to evaluate trends in 15 years of data on benthic macroinvertebrate communities from 17 Precambrian Shield lakes. We also used the van Belle and Hughes test of trend homogeneity to assess whether common among-lake temporal trends existed. We assumed that evidence of a common regional trend among lakes would support the hypothesis of long-term biological recovery from past acidification. We found decreasing proportions of Chironomidae and increasing proportions of Ephemeroptera, Plecoptera, and Trichoptera (EPT) in both single-lake and multi-lake trend analysis. Moreover, six of the nine lakes with significant trends in more than one benthos metric displayed a significant decrease in Chironomidae and increase in EPT concurrently, indicating a shift towards more acid-sensitive taxa. Weak trends in several of the biological metrics indicated that recovery in these lakes has been impeded. Results of this study indicate that the Mann-Kendall and van Belle and Hughes trend tests are useful statistical tools to evaluate long-term patterns in biological data.

Isotopic character of nitrous oxide emitted from streams.

Global models have indicated agriculturally impacted rivers and streams may be important sources of the greenhouse gas nitrous oxide (N(2)O). However, there is significant uncertainty in N(2)O budgets. Isotopic characterization can be used to help constrain N(2)O budgets. We present the first published measurements of the isotopic character of N(2)O emitted from low (2-4) order streams. Isotopic character of N(2)O varied seasonally, among streams, and over diel periods. On an annual basis, δ(18)O of emitted N(2)O (+47.4 to +51.4‰; relative to VSMOW) was higher than previously reported for larger rivers, but δ(15)N of emitted N(2)O (-16.2 to +2.4‰ among streams; relative to atmospheric N(2)) was similar to that of past studies. On an annual basis, all streams emitted N(2)O with lower δ(15)N than tropospheric N(2)O. Given these streams have elevated nitrate concentrations which are associated with enhanced N(2)O fluxes, this supports the hypothesis that streams are contributing to the accumulation of (15)N-depleted N(2)O in the troposphere.

Humic substances-part 7: the biogeochemistry of dissolved organic carbon and its interactions with climate change.

BACKGROUND, AIM, AND SCOPE: Dissolved organic matter, measured as dissolved organic carbon (DOC), is an important component of aquatic ecosystems and of the global carbon cycle. It is known that changes in DOC quality and quantity are likely to have ecological repercussions. This review has four goals: (1) to discuss potential mechanisms responsible for recent changes in aquatic DOC concentrations; (2) to provide a comprehensive overview of the interactions between DOC, nutrients, and trace metals in mainly boreal environments; (3) to explore the impact of climate change on DOC and the subsequent effects on nutrients and trace metals; and (4) to explore the potential impact of DOC cycling on climate change. MAIN FEATURES: We review recent research on the mechanisms responsible for recent changes in aquatic DOC concentrations, DOC interactions with trace metals, N, and P, and on the possible impacts of climate change on DOC in mainly boreal lakes. We then speculate on how climate change may affect DOC export and in-lake processing and how these changes might alter nutrient and metal export and processing. Furthermore, the potential impacts of changing DOC cycling patterns on climate change are examined. RESULTS: It has been noted that DOC concentrations in lake and stream waters have increased during the last 30 years across much of Europe and North America. The potential reasons for this increase include increasing atmospheric CO(2) concentration, climate warming, continued N deposition, decreased sulfate deposition, and hydrological changes due to increased precipitation, droughts, and land use changes. Any change in DOC concentrations and properties in lakes and streams will also impact the acid-base chemistry of these waters and, presumably, the biological, chemical, and photochemical reactions taking place. For example, the interaction of trace metals with DOC may be significantly altered by climate change as organically complexed metals such as Cu, Fe, and Al are released during photo-oxidation of DOC. The production and loss of DOC as CO(2) from boreal lakes may also be affected by changing climate. Climate change is unlikely to be uniform spatially with some regions becoming wetter while others become drier. As a result, rates of change in DOC export and concentrations will vary regionally and the changes may be non-linear. DISCUSSION: Climate change models predict that higher temperatures are likely to occur over most of the boreal forests in North America, Europe, and Asia over the next century. Climate change is also expected to affect the severity and frequency of storm and drought events. Two general climate scenarios emerge with which to examine possible DOC trends: warmer and wetter or warmer and drier. Increasing temperature and hydrological changes (specifically, runoff) are likely to lead to changes in the quality and quantity of DOC export from terrestrial sources to rivers and lakes as well as changes in DOC processing rates in lakes. This will alter the quality and concentrations of DOC and its constituents as well as its interactions with trace metals and the availability of nutrients. In addition, export rates of nutrients and metals will also change in response to changing runoff. Processing of DOC within lakes may impact climate depending on the extent to which DOC is mineralized to dissolved inorganic carbon (DIC) and evaded to the atmosphere or settles as particulate organic carbon (POC) to bottom sediments and thereby remaining in the lake. The partitioning of DOC between sediments and the atmosphere is a function of pH. Decreased DOC concentrations may also limit the burial of sulfate, as FeS, in lake sediments, thereby contributing acidity to the water by increasing the formation of H(2)S. Under a warmer and drier scenario, if lake water levels fall, previously stored organic sediments may be exposed to greater aeration which would lead to greater CO(2) evasion to the atmosphere. The interaction of trace metals with DOC may be significantly altered by climate change. Iron enhances the formation of POC during irradiation of lake water with UV light and therefore may be an important pathway for transfer of allochthonous DOC to the sediments. Therefore, changing Fe/DOC ratios could affect POC formation rates. If climate change results in altered DOC chemistry (e.g., fewer and/or weaker binding sites) more trace metals could be present in their toxic and bioavailable forms. The availability of nutrients may be significantly altered by climate change. Decreased DOC concentrations in lakes may result in increased Fe colloid formation and co-incident loss of adsorbable P from the water column. CONCLUSIONS: Climate change expressed as changes in runoff and temperature will likely result in changes in aquatic DOC quality and concentration with concomitant effects on trace metals and nutrients. Changes in the quality and concentration of DOC have implications for acid-base chemistry and for the speciation and bioavailability of certain trace metals and nutrients. Moreover, changes in DOC, metals, and nutrients are likely to drive changes in rates of C evasion and storage in lake sediments. RECOMMENDATIONS AND PERSPECTIVES: The key controls on allochthonous DOC quality, quantity, and catchment export in response to climate change are still not fully understood. More detailed knowledge of these processes is required so that changes in DOC and its interactions with nutrients and trace metals can be better predicted based on changes caused by changing climate. More studies are needed concerning the effects of trace metals on DOC, the effects of changing DOC quality and quantity on trace metals and nutrients, and how runoff and temperature-related changes in DOC export affect metal and nutrient export to rivers and lakes.

Detecting the transport of toxic pesticides from golf courses into watersheds in the Precambrian Shield region of Ontario, Canada.

Golf courses impact the environment through alterations to habitat and through the release of nutrients and pesticides. The Precambrian Shield region of central Ontario, Canada, which is a major recreational area, is especially susceptible to the impacts of golf courses as a result of the geology and hydrology of the region. In a monitoring program at two golf courses in the Muskoka region conducted during the spring, summer, and fall of 2002, semipermeable membrane devices (SPMDs) were deployed into streams that drain the golf courses. The extracts from the SPMDs were tested for toxicity using bioassays with early life stages of an aquarium fish, the Japanese medaka (Oryzias latipes). Toxicity was assessed using a scoring system developed for the present study. The bioassays with medaka indicated that toxicity was highest in extracts from SPMDs deployed during the spring and the fall. The peaks in toxicity for the SPMDs deployed at the two golf courses corresponded with the presence in the SPMD extracts of pentachloronitrobenzene (PCNB) at concentrations up to 334 ng/SPMD. Quintozene is the turfgrass fungicide in which PCNB is the active ingredient. Pentachlorothioanisole, an anaerobic degradation product of PCNB, also was detected in the SPMDs deployed during the spring. Extracts prepared from SPMDs with high toxicity contained residues of a surfactant used in pesticide formulations, nonylphenol, at concentrations up to approximately 20 microg/SPMD. Overall, these data indicate that some pesticides applied to golf courses in the Precambrian Shield of central Ontario may have the potential to cause toxic impacts to aquatic organisms in adjacent watersheds.

Decay of endocrine-disrupting chemicals in aerobic and anoxic groundwater.

Biodegradation and adsorption of selected endocrine-disrupting chemicals (EDCs), namely oestrogens (E2 and EE2) and phenolic compounds (BPA, 4-t-OP and 4-n-NP), in aquifer materials was investigated in the laboratory in order to understand the behaviour and fate of these chemicals associated with reclaimed water during managed aquifer recharge. Biodegradation experiments were conducted in microcosms with aquifer material and groundwater mixture, or with aquifer material and effluent mixture in the presence of glucose under both aerobic and anoxic conditions. All five selected compounds were degraded by microorganisms in both types of aquifer material-water mixtures under aerobic and anoxic conditions. Under aerobic conditions, EE2 was found to degrade faster in the aquifer material supplemented with effluent with a half-life of 15 days compared with that of 26 days in the aquifer material and groundwater microcosm. No significant difference between the two aquifer material-water mixtures was found for the other four compounds with half-lives ranging between 0.2 and 4.1 days. Under anoxic conditions, however, little biodegradation was observed for the selected EDCs except for E2, which degraded in the aquifer material in the presence of both water types.

Drought-induced sulphate release from a wetland in south-central Ontario.

Increased sulphate (SO(4)) export from wetlands following summer droughts in central Ontario, Canada has been associated with the delayed chemical recovery of downstream surface waters following decreased sulphur (S) emissions. Prolonged summer droughts result in a decrease or cessation of stream flow, declines in wetland water table level and oxidation of reduced S compounds to SO(4), which is subsequently flushed into drainage streams when stream flow resumes. Sulphate input-output budget calculations (1983-1995 and 1999-2001) at a conifer Sphagnum swamp in the Plastic Lake catchment, indicate that SO(4) is retained in most years but is exported on a net basis following particularly severe summer droughts that result in the cessation of stream flow for more than 54 days (95% CI: 41-72 days). Hindcast calculations using long-term (1916-2000) stream discharge records from a nearby station indicate that while droughts occurred frequently in south-central Ontario over the past 85 years, sufficiently dry conditions to cause net SO(4) export occurred in only 18 of the past 85 years, and indicate a cumulative positive SO(4) balance for the swamp (i.e. net SO(4) retention). Furthermore, the S pool at the Plastic Lake swamp has been estimated to be approximately 1500 kg S/ha in the upper 40 cm peat layer, which is large compared to the amount of net SO(4) export that occurs even in years with particularly dry summers (e.g. -43 kg S/ha in 1987/88). Together, these data suggest that the wetland S pool at Plastic Lake has not been depleted by previous droughts and will continue to sustain episodic drought-related SO(4) export for the foreseeable future.

Spectrofluorometric properties of dissolved organic matter from Central and Southern Ontario streams and the influence of iron and irradiation.

Fluorescence measurements were used to compare characteristics of dissolved organic matter (DOM) from distinctly different origins: boreal, agricultural and urban streams as well as a storm runoff pond and the outlet of a tertiary wastewater treatment plant. The primary goal was to determine if differences among stream types could be detected using DOM fluorescence in lieu of isolated fulvic acids (FA). Differences in peak excitation and peak emission wavelengths, fluorescence integrated over the 3-D matrix volume integrated fluorescence (VIF), and in a fluorescence index (FI) were examined. In general, peak fluorescence excitation and emission wavelengths as well as FI best distinguished DOM from the various origins. Results suggested that DOM from the boreal streams was of a higher molecular weight and more complex than that of agricultural and urban streams. The effects of irradiation as well as Fe on fluorescence of natural stream waters were also investigated, both of which decreased the ability of optical properties to distinguish DOM source.

Multiscale characterization of a heterogeneous aquifer using an ASR operation.

Heterogeneity in the physical properties of an aquifer can significantly affect the viability of aquifer storage and recovery (ASR) by reducing the recoverable proportion of low-salinity water where the ambient ground water is brackish or saline. This study investigated the relationship between knowledge of heterogeneity and predictions of solute transport and recovery efficiency by combining permeability and ASR-based tracer testing with modeling. Multiscale permeability testing of a sandy limestone aquifer at an ASR trial site showed that small-scale core data give lower-bound estimates of aquifer hydraulic conductivity (K), intermediate-scale downhole flowmeter data offer valuable information on variations in K with depth, and large-scale pumping test data provide an integrated measure of the effective K that is useful to constrain ground water models. Chloride breakthrough and thermal profiling data measured during two cycles of ASR showed that the movement of injected water is predominantly within two stratigraphic layers identified from the flowmeter data. The behavior of the injectant was reasonably well simulated with a four-layer numerical model that required minimal calibration. Verification in the second cycle achieved acceptable results given the model's simplicity. Without accounting for the aquifer's layered structure, high precision could be achieved on either piezometer breakthrough or recovered water quality, but not both. This study demonstrates the merit of an integrated approach to characterizing aquifers targeted for ASR.

Comparative evaluation of the fate of disinfection byproducts at eight aquifer storage and recovery sites.

Despite the growth in aquifer storage and recovery (ASR) as a technique for the provision of potable water supplies, quantitative data on the fate of disinfection byproducts that may be present in the injected water remain rare. This study evaluates the data from eight ASR sites in Australia and the United States that cover a wide range of source water compositions, hydrogeological environments, and operating conditions. Rates of attenuation and formation of trihalomethanes (THMs) in groundwater were determined using analytical techniques that took dilution effects into account. Half-lives varied by more than 2 orders of magnitude (e.g., <1 to >120 days for total THMs) and were both compound- and site- specific. Chloroform was most persistent, and more highly brominated compounds tended to be less persistent, as has generally been found. For any particular THM compound, much of the variability could be explained by contrasts in geochemical conditions within the aquifer since microbial degradation is the primary mechanism for THM attenuation. As such, bounds on the half-life were defined according to the redox state of the groundwater. In situ formation of some THMs in the aquifer after injection was directly observed at a number of sites, and was predicted to have taken place at all sites. The variance in formation estimates was large between the different methods used. Formation may be more common than previously thought because of the low frequency of groundwater sampling after injection and concomitant attenuation and mixing.

Export of nutrients from golf courses on the Precambrian Shield.

Annual export rates, or fluxes, of total nitrogen (TN), nitrate, total phosphorus (TP) and potassium from four streams on two golf courses on the Precambrian Shield were compared with those from forested reference locations. Overall, the mean annual fluxes of K, TN, NO(3) and TP from golf courses were greater than from forested areas by 10, 2, 6 and 2 times, respectively. The overall mean export coefficients (kg/ha/yr) were 16 for K, 5.2 for TN, 2.1 for NO(3) and 0.14 for TP. For TN and TP, these are similar to those reported from cropland in Canada by Chambers and Dale.

Effect of declining lake base cation concentration on freshwater critical load calculations.

Steady-state critical load models have been extensively used as the scientific underpinning for air pollution control policies in Europe and are currently being applied to other parts of the world. An important assumption of steady-state models is that critical load estimates do not change through time (or time scale of interest). The most commonly used model for estimating freshwater critical loads is the steady-state water chemistry (SSWC) model. In this study we examined changes in SSWC critical load estimates for 29 lakes in south-central Ontario using data collected 13 years apart (1985-1998), during which time bulk sulfate (SO4(2-)) deposition decreased by 35%. In lakes with the lowest base cation concentrations (<120 microequiv L(-1) Ca2+), the decrease in SO4(2-) concentration was accompanied by an approximately equivalent decrease in base cation concentration, resulting in only a minimal increase in Acid Neutralizing Capacity (ANC) during the 13-year period (median increase 1.6 microequiv L(-1)), and the median critical load for acidity (CL(A)) estimated by the SSWC model decreased by 14.6%. These changes may have been brought about by declining base cation concentrations owing to continued soil acidification in the region. In contrast, in lakes with higher base cation concentrations (>150 microequiv L(-1) Ca2+), the relative decline in base cation concentration was not as great, resulting in a larger increase in ANC (median increase 13.1 microequiv L(-1)) and an increase in the estimated CL(A) (median 5.1%). Lakes with moderate base cation concentrations (120-150 microequiv L(-1) Ca2+) exhibited an intermediate response; the median ANC increased by 8.8 microequiv L(-1) and the estimated CL-(A) decreased by 2.2%. In central Ontario, SSWC critical load estimates based on data taken only 13 years apart change quite dramatically due to changing lake base cation concentrations, and the response appears to depend on the base status of the lakes. The changing values obtained from the SSWC model have important consequences for policy decisions regarding acceptable levels of acid deposition. The application of dynamic models that take into account changes in lake/soil chemistry appears more appropriate for estimating acceptable levels of acid deposition in the region.

Fate of disinfection by-products in groundwater during aquifer storage and recovery with reclaimed water.

Knowledge on the behaviour of disinfection by-products (DBPs) during aquifer storage and recovery (ASR) is limited even though this can be an important consideration where recovered waters are used for potable purposes. A reclaimed water ASR trial in an anoxic aquifer in South Australia has provided some of the first quantitative information at field-scale on the fate and transport of trihalomethanes (THMs) and haloacetic acids (HAAs). The results revealed that THM half-lives varied from <1 to 65 days, with persistence of chloroform being highest and bromoform lowest. HAA attenuation was rapid (<1 day). Rates of THM attenuation were shown to be highly dependent on the geochemical environment as evidenced by the 2-5 fold reduction in half-lives at the ASR well which became methanogenic during the storage phase of the trial, as compared to an observation well situated 4 m away, which remained nitrate-reducing. These findings agree with previous laboratory-based studies which also show persistence declining with increased bromination of THMs and reducing redox conditions. Modelling suggests that the chlorinated injectant has sufficient residual chlorine and natural organic matter for substantial increases in THMs to occur within the aquifer, however this is masked in some of the field observations due to concurrent attenuation, particularly for the more rapidly attenuated brominated compounds. The model is based on data taken from water distribution systems and may not be representative for ASR since bromide and ammonia concentrations in the injected water and the possible role of organic carbon in the aquifer were not taken into consideration. During the storage phase DBP formation potentials were reduced as a result of the removal of precursor material despite an increase in the THM formation potential per unit weight of total organic carbon. This suggests that water quality improvements with respect to THMs and HAAs can be achieved through ASR in anoxic aquifers.