The extensive use of road salts as deicers during winter months is causing the salinization of freshwater systems in cold climate regions worldwide. We analyzed 20 years (2001–2020) of data on lake water chemistry, land cover changes, and road salt applications for Lake Wilcox (LW) located in southern Ontario, Canada. The lake is situated within a rapidly urbanizing watershed in which, during the period of observation, on average 785 tons of road salt were applied annually. However, only about a quarter of this salt has reached the lake so far. That is, most salt has been retained in the watershed, likely through accumulation in soils and groundwater. Despite the high watershed salt retention, time series trend analyses for LW show significant increases in the dissolved concentrations of sodium (Na+) and chloride (Cl−), as well as those of sulfate (SO42−), calcium (Ca2+), and magnesium (Mg2+). The relative changes in the major ion concentrations indicate a shift of the lake water chemistry from the mixed SO42–Cl–Ca2+-Mg2+ type to the Na + -Cl- type. Salinization of LW has further been strengthening and lengthening the lake's summer stratification, which, in turn, has been enhancing hypoxia in the hypolimnion and increasing the internal loading of the limiting nutrient phosphorus. The theoretical salinity threshold at which fall overturn would become increasingly unlikely was estimated at around 1.23 g kg−1. A simple chloride mass balance model predicts that, under the current trend of impermeable land cover expansion, LW could reach this salinity threshold by mid-century. Our results also highlight the need for additional research on the accruing salt legacies in urbanizing watersheds because they represent potential long-term threats to water quality for receiving freshwater ecosystems and regional groundwater resources.

A sufficient supply of dissolved silicon (DSi) relative to dissolved phosphorus (DP) may decrease the likelihood of harmful algal blooms in eutrophic waters. Oxidative precipitation of Fe(II) at oxic-anoxic interfaces may contribute to the immobilization of DSi, thereby exerting control over the DSi availability in the overlying water. Nevertheless, the efficacy of DSi immobilization in this context remains to be precisely determined. To investigate the behavior of DSi during Fe(II) oxidation, anoxic solutions containing mixtures of aqueous Fe(II), DSi, and dissolved phosphorus (DP) were exposed to dissolved oxygen (DO) in the batch system. The experimental data, combined with kinetic reaction modeling, indicate that DSi removal during Fe(II) oxidation occurs via two pathways. At the beginning of the experiments, the oxidation of Fe(II)-DSi complexes induces the fast removal of DSi. Upon complete oxidation of Fe(II), further DSi removal is due to adsorption to surface sites of the Fe(III) oxyhydroxides. The presence of DP effectively competes with DSi via both of these pathways during the initial and later stages of the experiments, with as a result more limited removal of DSi during Fe(II) oxidation. Overall, we conclude that at near neutral pH the oxidation of Fe(II) has considerable capacity to immobilize DSi, where the rapid homogeneous oxidation of Fe(II)-DSi results in greater DSi removal compared to surface adsorption. Elevated DP concentration, however, effectively outcompetes DSi in co-precipitation interactions, potentially contributing to enhanced DSi availability within aquatic systems.

Stormwater ponds (SWPs) alter the export of the macronutrient phosphorus (P) from urban landscapes, hence impacting the trophic state and water quality of downstream aquatic environments.

Cold regions are warming much faster than the global average, resulting in more frequent and intense freeze-thaw cycles (FTCs) in soils. In hydrocarbon-contaminated soils, FTCs modify the biogeochemical and physical processes controlling petroleum hydrocarbon (PHC) biodegradation and the associated generation of methane (CH4) and carbon dioxide (CO2). Thus, understanding the effects of FTCs on the biodegradation of PHCs is critical for environmental risk assessment and the design of remediation strategies for contaminated soils in cold regions. In this study, we developed a diffusion-reaction model that accounts for the effects of FTCs on toluene biodegradation, including methanogenic biodegradation. The model is verified against data generated in a 215 day-long batch experiment with soil collected from a PHC contaminated site in Ontario, Canada. The fully saturated soil incubations with six different treatments were exposed to successive 4-week FTCs, with temperatures oscillating between −10 °C and +15 °C, under anoxic conditions to stimulate methanogenic biodegradation. We measured the headspace concentrations and 13C isotope compositions of CH4 and CO2 and analyzed the porewater for pH, acetate, dissolved organic and inorganic carbon, and toluene. The numerical model represents solute diffusion, volatilization, sorption, as well as a reaction network of 13 biogeochemical processes. The model successfully simulates the soil porewater and headspace concentration time series data by representing the temperature dependencies of microbial reaction and gas diffusion rates during FTCs. According to the model results, the observed increases in the headspace concentrations of CH4 and CO2 by 87% and 136%, respectively, following toluene addition are explained by toluene fermentation and subsequent methanogenesis reactions. The experiment and the numerical simulation show that methanogenic degradation is the primary toluene attenuation mechanism under the electron acceptor-limited conditions experienced by the soil samples, representing 74% of the attenuation, with sorption contributing to 11%, and evaporation contributing to 15%. Also, the model-predicted contribution of acetate-based methanogenesis to total produced CH4 agrees with that derived from the 13C isotope data. The freezing-induced soil matrix organic carbon release is considered as an important process causing DOC increase following each freezing period according to the calculations of carbon balance and SUVA index. The simulation results of a no FTC scenario indicate that, in the absence of FTCs, CO2 and CH4 generation would decrease by 29% and 26%, respectively, and that toluene would be biodegraded 23% faster than in the FTC scenario. Because our modeling approach represents the dominant processes controlling PHC biodegradation and the associated CH4 and CO2 fluxes, it can be used to analyze the sensitivity of these processes to FTC frequency and duration driven by temperature fluctuations.

Cold regions are warming much faster than the global average, resulting in more frequent and intense freeze-thaw cycles (FTCs) in soils. In hydrocarbon-contaminated soils, FTCs modify the biogeochemical and physical processes controlling petroleum hydrocarbon (PHC) biodegradation and the associated generation of methane (CH4) and carbon dioxide (CO2). Thus, understanding the effects of FTCs on the biodegradation of PHCs is critical for environmental risk assessment and the design of remediation strategies for contaminated soils in cold regions. In this study, we developed a diffusion-reaction model that accounts for the effects of FTCs on toluene biodegradation, including methanogenic biodegradation. The model is verified against data generated in a 215 day-long batch experiment with soil collected from a PHC contaminated site in Ontario, Canada. The fully saturated soil incubations with six different treatments were exposed to successive 4-week FTCs, with temperatures oscillating between −10 °C and +15 °C, under anoxic conditions to stimulate methanogenic biodegradation. We measured the headspace concentrations and 13C isotope compositions of CH4 and CO2 and analyzed the porewater for pH, acetate, dissolved organic and inorganic carbon, and toluene. The numerical model represents solute diffusion, volatilization, sorption, as well as a reaction network of 13 biogeochemical processes. The model successfully simulates the soil porewater and headspace concentration time series data by representing the temperature dependencies of microbial reaction and gas diffusion rates during FTCs. According to the model results, the observed increases in the headspace concentrations of CH4 and CO2 by 87% and 136%, respectively, following toluene addition are explained by toluene fermentation and subsequent methanogenesis reactions. The experiment and the numerical simulation show that methanogenic degradation is the primary toluene attenuation mechanism under the electron acceptor-limited conditions experienced by the soil samples, representing 74% of the attenuation, with sorption contributing to 11%, and evaporation contributing to 15%. Also, the model-predicted contribution of acetate-based methanogenesis to total produced CH4 agrees with that derived from the 13C isotope data. The freezing-induced soil matrix organic carbon release is considered as an important process causing DOC increase following each freezing period according to the calculations of carbon balance and SUVA index. The simulation results of a no FTC scenario indicate that, in the absence of FTCs, CO2 and CH4 generation would decrease by 29% and 26%, respectively, and that toluene would be biodegraded 23% faster than in the FTC scenario. Because our modeling approach represents the dominant processes controlling PHC biodegradation and the associated CH4 and CO2 fluxes, it can be used to analyze the sensitivity of these processes to FTC frequency and duration driven by temperature fluctuations.

Abstract Sediment core and water quality data, together with historical information on land use/land cover (LULC), were used to reconstruct changes in phosphorus (P) loading and cycling in Lake Wilcox, Ontario, Canada, since the early 1920s. After first being cleared for farming, the originally forested watershed subsequently underwent urbanization. The large increase in P loading accompanying agricultural intensification after World War II caused the eutrophication of the lake. However, improved soil conservation since the 1980s and urban stormwater management since the 1990s have brought watershed P loading and sediment accumulation down to levels comparable to the early 1900s. Yet, the lake continues to exhibit eutrophication‐like symptoms, especially the intensification of hypoxia in the hypolimnion. Post‐2000 water quality data indicate that the latter is not driven by external P loading from the watershed, but rather by rapid salinization that strengthens the lake's summer stratification and enhances internal P loading. Salinization is caused by the increasing application of deicing agents in the expanding urban area. Curbing salt inputs will therefore be essential to restore the lake. Overall, our results provide new insights into the shifts in lake biogeochemistry associated with LULC changes and the implementation of best management practices. The approaches and findings of our case study have broad applicability for the large number of freshwater ecosystems worldwide that are experiencing salinization.

Abstract Sediment core and water quality data, together with historical information on land use/land cover (LULC), were used to reconstruct changes in phosphorus (P) loading and cycling in Lake Wilcox, Ontario, Canada, since the early 1920s. After first being cleared for farming, the originally forested watershed subsequently underwent urbanization. The large increase in P loading accompanying agricultural intensification after World War II caused the eutrophication of the lake. However, improved soil conservation since the 1980s and urban stormwater management since the 1990s have brought watershed P loading and sediment accumulation down to levels comparable to the early 1900s. Yet, the lake continues to exhibit eutrophication‐like symptoms, especially the intensification of hypoxia in the hypolimnion. Post‐2000 water quality data indicate that the latter is not driven by external P loading from the watershed, but rather by rapid salinization that strengthens the lake's summer stratification and enhances internal P loading. Salinization is caused by the increasing application of deicing agents in the expanding urban area. Curbing salt inputs will therefore be essential to restore the lake. Overall, our results provide new insights into the shifts in lake biogeochemistry associated with LULC changes and the implementation of best management practices. The approaches and findings of our case study have broad applicability for the large number of freshwater ecosystems worldwide that are experiencing salinization.

The rapid growth in microplastic pollution research is influencing funding priorities, environmental policy, and public perceptions of risks to water quality and environmental and human health. Ensuring that environmental microplastics research data are findable, accessible, interoperable, and reusable (FAIR) is essential to inform policy and mitigation strategies. We present a bibliographic analysis of data sharing practices in the environmental microplastics research community, highlighting the state of openness of microplastics data. A stratified (by year) random subset of 785 of 6,608 microplastics articles indexed in Web of Science indicates that, since 2006, less than a third (28.5%) contained a data sharing statement. These statements further show that most often, the data were provided in the articles’ supplementary material (38.8%) and only 13.8% via a data repository. Of the 279 microplastics datasets found in online data repositories, 20.4% presented only metadata with access to the data requiring additional approval. Although increasing, the rate of microplastic data sharing still lags behind that of publication of peer-reviewed articles on environmental microplastics. About a quarter of the repository data originated from North America (12.8%) and Europe (13.4%). Marine and estuarine environments are the most frequently sampled systems (26.2%); sediments (18.8%) and water (15.3%) are the predominant media. Of the available datasets accessible, 15.4% and 18.2% do not have adequate metadata to determine the sampling location and media type, respectively. We discuss five recommendations to strengthen data sharing practices in the environmental microplastic research community.

Abstract. Lakes are key ecosystems within the global biogeosphere. However, the environmental controls on the biological productivity of lakes – including surface temperature, ice phenology, nutrient loads, and mixing regime – are increasingly altered by climate warming and land-use changes. To better characterize global trends in lake productivity, we assembled a dataset on chlorophyll-a concentrations as well as associated water quality parameters and surface solar radiation for temperate and cold-temperate lakes experiencing seasonal ice cover. We developed a method to identify periods of rapid net increase of in situ chlorophyll-a concentrations from time series data and applied it to data collected between 1964 and 2019 across 343 lakes located north of 40∘. The data show that the spring chlorophyll-a increase periods have been occurring earlier in the year, potentially extending the growing season and increasing the annual productivity of northern lakes. The dataset on chlorophyll-a increase rates and timing can be used to analyze trends and patterns in lake productivity across the northern hemisphere or at smaller, regional scales. We illustrate some trends extracted from the dataset and encourage other researchers to use the open dataset for their own research questions. The PCI dataset and additional data files can be openly accessed at the Federated Research Data Repository at https://doi.org/10.20383/102.0488 (Adams et al., 2021).

The availability of dissolved silicon (DSi) exerts an important control on phytoplankton communities in freshwater environments: DSi limitation can shift species dominance to non-siliceous algae and increase the likelihood of harmful algal blooms. The availability of DSi in the water column in turn depends on the dissolution kinetics of amorphous silica (ASi), including diatoms frustules and phytoliths. Here, batch dissolution experiments conducted with diatom frustules from three diatom species and synthetic Aerosil OX 50 confirmed the previously reported non-linear dependence of ASi dissolution rate on the degree of undersaturation of the aqueous solution. At least two first-order dissolution rate constants are therefore required to describe the dissolution kinetics at high (typically, ≥0.55) and low (typically, <0.55) degrees of undersaturation. Our results further showed aqueous ferrous ion (Fe2+), which is ubiquitous in anoxic waters, strongly inhibited ASi dissolution. The inhibition is attributed to the preferential binding of Fe2+ to Q2 groups (i.e., surface silicate groups bonded to the silica lattice via two bridging oxygen) which stabilizes the silica surface. However, further increasing the aqueous Fe2+ concentration likely catalyzes the detachment of Q3 groups (i.e., silicate groups bonded to the silica lattice via three bridging oxygen) from the surface. Overall, our study illustrates the manyfold effects the aqueous solution composition, notably the inhibition effect of Fe2+ under anoxic conditions, has on ASi dissolution. The results help to explain the controversial redox dependence of DSi internal loading from sediments, which is vital to quantitatively understanding silicon (Si) cycling in freshwater systems.

Lake Wilcox (LW), a shallow kettle lake located in southern Ontario, has experienced multiple phases of land use change associated with human settlement and residential development in its watershed since the early 1900s. Urban growth has coincided with water quality deterioration, including the occurrence of algal blooms and depletion of dissolved oxygen (DO) in the water column. We analyzed 22 years of water chemistry, land use, and climate data (1996-2018) using principal component analysis (PCA) and multiple linear regression (MLR) to identify the contributions of climate, urbanization, and nutrient loading to the changes in water chemistry. Variations in water column stratification, phosphorus (P) speciation, and chl-a (as a proxy for algal abundance) explain 76 % of the observed temporal trends of the four main PCA components derived from water chemistry data. MLR results further imply that the intensity of stratification, quantified by the Brunt-Väisälä frequency, is a major predictor of the changes in water quality. Other important factors explaining the variations in nitrogen (N) and P speciation, and the DO concentrations, are watershed imperviousness and lake chloride concentrations that, in turn, are closely correlated. We conclude that the observed in-lake water quality trends over the past two decades are linked to urbanization via increased salinization associated with expanding impervious land cover, rather than increasing external P loading. The rising salinity promotes water column stratification, which reduces the oxygenation of the hypolimnion and enhances internal P loading to the water column. Thus, stricter controls on the application and runoff of de-icing salt should be considered as part of managing eutrophication symptoms in lakes of cold climate regions.

Peat accumulation in high latitude wetlands represents a natural long-term carbon sink, resulting from the cumulative excess of growing season net ecosystem production over non-growing season (NGS) net mineralization in soils. With high latitudes experiencing warming at a faster pace than the global average, especially during the NGS, a major concern is that enhanced mineralization of soil organic carbon will steadily increase CO2 emissions from northern peatlands. In this study, we conducted laboratory incubations with soils from boreal and temperate peatlands across Canada. Peat soils were pretreated for different soil moisture levels, and CO2 production rates were measured at 12 sequential temperatures, covering a range from - 10 to + 35 °C including one freeze-thaw event. On average, the CO2 production rates in the boreal peat samples increased more sharply with temperature than in the temperate peat samples. For same temperature, optimum soil moisture levels for CO2 production were higher in the peat samples from more flooded sites. However, standard reaction kinetics (e.g., Q10 temperature coefficient and Arrhenius equation) failed to account for the apparent lack of temperature dependence of CO2 production rates measured below 0 °C, and a sudden increase after a freezing event. Thus, we caution against using the simple kinetic expressions to represent the CO2 emissions from northern peatlands, especially regarding the long NGS period with multiple soil freeze and thaw events.

This code, developed in MATLAB R2018a, is a process based mass balance modelfor simulating the biogeochemical cycling of nitrogen in dam reservoirs.

Groundwater discharge can be a major source of nutrients to river systems. Although quantification of groundwater nitrate loading to streams is common, the dependence of surface water silicon (Si) and phosphorus (P) concentrations on groundwater sources has rarely been determined. Additionally, the ability of groundwater discharge to drive surface water Si:P ratios has not been contextualized relative to riverine inputs or in-stream transformations. In this study, we quantify the seasonal dynamics of Si and P cycles in the Grand River (GR) watershed, the largest Canadian watershed draining into Lake Erie, to test our hypothesis that regions of Si-rich groundwater discharge increase surface water Si:P ratios. Historically, both the GR and Lake Erie have been considered stoichiometrically P-limited, where the molar Si:P ratio is greater than the ~16:1 phytoplankton uptake ratio. However, recent trends suggest that eastern Lake Erie may be approaching Si-limitation. We sampled groundwater and surface water for dissolved and reactive particulate Si as well as total dissolved P for 12months within and downstream of a 50-km reach of high groundwater discharge. Our results indicate that groundwater Si:P ratios are lower than the corresponding surface water and that groundwater is a significant source of bioavailable P to surface water. Despite these observations, the watershed remains P-limited for the majority of the year, with localized periods of Si-limitation. We further find that groundwater Si:P ratios are a relatively minor driver of surface water Si:P, but that the magnitude of Si and P loads from groundwater represent a large proportion of the overall fluxes to Lake Erie.