Catalytic and biocatalytic degradation of microplastics.

In recent years, there has been a surge in annual plastic production, which has contributed to growing environmental challenges, particularly in the form of microplastics. Effective management of plastic and microplastic waste has become a critical concern, necessitating innovative strategies to address its impact on ecosystems and human health. In this context, catalytic degradation of microplastics emerges as a pivotal approach that holds significant promise for mitigating the persistent effects of plastic pollution. In this article, we critically explored the current state of catalytic degradation of microplastics and discussed the definition of degradation, characterization methods for degradation products, and the criteria for standard sample preparation. Moreover, the significance and effectiveness of various catalytic entities, including enzymes, transition metal ions (for the Fenton reaction), nanozymes, and microorganisms are summarized. Finally, a few key issues and future perspectives regarding the catalytic degradation of microplastics are proposed.

Impact of freeze-thaw cycles on greenhouse gas emissions in marginally productive agricultural land under different perennial bioenergy crops.

Knowledge of freeze-thaw-induced carbon (C) and nitrogen (N) cycling and concomitant nitrous oxide (N2O) and carbon dioxide (CO2) emissions in perennial bioenergy crops is crucial to understanding the contribution of these crops in mitigating climate change through reduced greenhouse gas (GHG) emissions. In this study, a 49-day laboratory incubation experiment was conducted to compare the impact of freeze-thaw cycles on N2O and CO2 emissions in different perennial bioenergy crops [miscanthus (Miscanthus giganteus L.), switchgrass (Panicum virgatum L.), and willow (Salix miyabeana L.)] to a successional site and to understand the processes controlling the N2O and CO2 emissions in these crops. The results showed that freeze-thaw cycles caused a decline in dissolved organic C (DOC) and dissolved inorganic N (DIN) concentrations but enhanced the dissolved organic N (DON) and nitrate (NO3-). Although, freeze-thaw decreased water stable soil aggregates in all the bioenergy crops and successional site, this did not have any significant impact on N2O and CO2 emissions, suggesting that the N2O and CO2 emitted during the freeze-thaw cycles may have originated mostly from cellular materials released from lysis and death of microbial biomass rather than from soil aggregate disruption. Cumulative N2O emissions measured over the 49-day incubation period ranged from 148 mg N2O-N m-2 to 17 mg N2O-N m-2 and were highest in miscanthus followed by willow, switchgrass, and successional site. Cumulative CO2 on the other hand was highest in the successional site than any of the bioenergy crops and ranged from 25,262 mg CO2-C m-2 to 15,403 mg CO2-C m-2 after the 49 days. Higher N2O emissions in the miscanthus and willow than switchgrass and successional site were attributed to accelerated N losses as N2O. Results from our study indicate that managing perennial bioenergy crops on low productive agricultural lands to reduce freeze-thaw related GHG emissions and climate change mitigation is dependent on the crop species grown.

Modeling multi-year phosphorus dynamics in a bioretention cell: Phosphorus partitioning, accumulation, and export.

Phosphorus (P) export from urban areas via stormwater runoff contributes to eutrophication of downstream aquatic ecosystems. Bioretention cells are a Low Impact Development (LID) technology promoted as a green solution to attenuate urban peak flow discharge, as well as the export of excess nutrients and other contaminants. Despite their rapidly growing implementation worldwide, a predictive understanding of the efficiency of bioretention cells in reducing urban P loadings remains limited. Here, we present a reaction-transport model to simulate the fate and transport of P in a bioretention cell facility in the greater Toronto metropolitan area. The model incorporates a representation of the biogeochemical reaction network that controls P cycling within the cell. We used the model as a diagnostic tool to determine the relative importance of processes immobilizing P in the bioretention cell. The model predictions were compared to multi-year observational data on 1) the outflow loads of total P (TP) and soluble reactive P (SRP) during the 2012-2017 period, 2) TP depth profiles collected at 4 time points during the 2012-2019 period, and 3) sequential chemical P extractions performed on core samples from the filter media layer obtained in 2019. Results indicate that exfiltration to underlying native soil was principally responsible for decreasing the surface water discharge from the bioretention cell (63 % runoff reduction). From 2012 to 2017, the cumulative outflow export loads of TP and SRP only accounted for 1 % and 2 % of the corresponding inflow loads, respectively, hence demonstrating the extremely high P reduction efficiency of this bioretention cell. Accumulation in the filter media layer was the predominant mechanism responsible for the reduction in P outflow loading (57 % retention of TP inflow load) followed by plant uptake (21 % TP retention). Of the P retained within the filter media layer, 48 % occurred in stable, 41 % in potentially mobilizable, and 11 % in easily mobilizable forms. There were no signs that the P retention capacity of the bioretention cell was approaching saturation after 7 years of operation. The reactive transport modeling approach developed here can in principle be transferred and adapted to fit other bioretention cell designs and hydrological regimes to estimate P surface loading reductions at a range of temporal scales, from a single precipitation event to long-term (i.e., multi-year) operation.

Effects of freeze-thaw cycles on methanogenic hydrocarbon degradation: Experiment and modeling.

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.

Salinization as a driver of eutrophication symptoms in an urban lake (Lake Wilcox, Ontario, Canada).

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.

Dissolution and remobilization of NAPL in surfactant-enhanced aquifer remediation from microscopic scale simulations.

In this paper, the dissolution and mobilization of non-aqueous phase liquid (NAPL) blobs in the Surfactant-Enhanced Aquifer Remediation (SEAR) process were upscaled using dynamic pore network modeling (PNM) of three-dimensional and unstructured networks. We considered corner flow and micro-flow mechanisms including snap-off and piston-like movement for two-phase flow. Moreover, NAPL entrapment and remobilization were evaluated using force analysis to develop the capillary desaturation curve (CDC) and predict the onset of remobilization. The corner diffusion mechanism was also applied in the modeling of interphase mass transfer to represent NAPL dissolution as the dominant mass transfer process. In addition, the effect of pore-scale heterogeneity on mass transfer rate coefficient and recovered residual NAPL was considered in the simulations. Sodium dodecyl sulfate (SDS) and Triton X-100 were used as the surfactant for the SEAR process. The results indicate that although surfactants enhance NAPL recovery during two-phase flow, surfactant-enhanced remediation of residual NAPL through dissolution is highly dependent on surfactant type. When SDS ─as a surfactant with high critical micelle concentration (CMC) and low micelle partition coefficient (Km)─ was injected into a NAPL contaminated site, the mass transfer rate coefficient decreased (due to considerable changes in interface chemical potentials) which leads to a significant reduction in NAPL recovery after the end of two-phase flow. In contrast, Triton X-100 (with low CMC and high Km) improved NAPL recovery, by enhancing solubility at surfactant concentrations greater than CMC which overcompensates the interphase mass transfer reduction.

Temperature, moisture and freeze-thaw controls on CO2 production in soil incubations from northern peatlands.

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.

Particle fractionation controls Escherichia coli release from solid manure.

Bacteria transport through soil is a complex process particularly when the cells are released from solid manures and co-transported with particles. This study focuses on understanding of the Escherichia coli release from different particle fractions (0.25-, 0.5-, 1-, and 2-mm) of solid manure and evaluating different influent boundary conditions during cell release from manure and when a solid manure is applied to the soil. The 0.25-mm and 2-mm particle sizes resulted a greater cell release compared to 0.5-mm and 1-mm fractions (p < 0.05). The shape and magnitude of the cell release curves (CRCs) from the original manure bulk were mainly influenced by the two 0.25-mm and 2-mm fractions, respectively. The arithmetic mean for normalizing the CRCs and the time variable- based normalized CRCs for the manure-treated soil were the robust variables in evaluation of the experimental data. However, a single maximum bacteria concentration could provide the realistic dataset for the modeling process. Evaluation of the root-mean-squared-error and Akaike criterion showed that the two- and three-parametric models are recommended for simulating the cell release from solid manure in comparison with one parametric models. This study also suggests considering separate microbial release evaluations, with regards to influent concentration, for manure and manure-treated soils to propose best management practices for controlling bacteria pollution. Further research will reveal the key roles of different woody components and soluble material ratios for the various solid manures in bacteria release.

Coupled hydrological and geochemical impacts of wildfire in peatland-dominated regions of discontinuous permafrost.

Naturally-ignited wildfires are increasing in frequency and severity in northern regions, contributing to rapid permafrost thaw-induced landscape change driven by climate warming. Low-severity wildfires typically result in minor organic matter loss. The impacts of such fires on the hydrological and geochemical dynamics of peat plateau-wetland complexes have not been examined. In 2014, a low-severity wildfire, with minimal ground surface damage, burned approximately one-half of a 5 ha permafrost plateau in the wetland-dominated landscape of the Scotty Creek watershed, Northwest Territories, Canada, in the discontinuous permafrost zone. In March 2016, hydrometeorological and permafrost conditions on the burned and unaffected plateaus were monitored including snowpack characteristics and surface energy dynamics. Pore water samples were collected from the saturated layer as thaw progressed throughout the growing season on the burned and unaffected plateaus. Repeated probing of the frost table depth was coupled with laboratory analyses of peat physical and hydraulic characteristics performed on peat cores collected from the top 20 cm of the ground surface in the burned and unaffected plots. The higher transmissivity of the burned forest canopy accelerated snowmelt promoting earlier onset of the thawing season and increased the ground heat flux to melt ground ice. Wildfire increased the thickness of the supra-permafrost layer, including the active layer and talik, resulting in a more uniform subsurface with limited depressional storage capacity and reduced preferential runoff flowpaths across the burned plateau. The incorporation of ash and char into the peat matrix reduced pore diameters, promoting greater subsurface soil moisture retention and longer pore water residence times ultimately providing greater opportunity for soil-water interaction and biogeochemical reactions. Consequently, pore water showed elevated dissolved solutes, dissolved organic matter and mercury concentrations in the burned site. Low-severity wildfires have the potential to trigger a series of complex, inter-related hydrological, thermal and biogeochemical processes and feedbacks.

Spatiotemporal geo-electrical sensing of a Pluronic-coated cobalt ferrite nanoparticle slug in natural sand flow-through columns.

Rising industrial interest in the application of nanomaterials for the remediation of contaminated sites has led to concern over the environmental fate of the nanoremediation agents used. A critical requirement in evaluating and understanding nanoparticle (NP) behaviour in porous media is the development of analytical methods capable of in situ monitoring of complex NP transport dynamics. Spectral induced polarization (SIP), a non-invasive geo-electrical technique, offers a promising tool for detecting and quantifying NPs in soil and aquifer media. However, its application for monitoring the spatial migration and attachment behaviour of NPs remains uninvestigated. Here, we present results from flow-through experiments where we monitored the transport of cobalt ferrite nanoparticles (CoFe-NPs) coated with Pluronic, an amphiphilic polymer, in natural aquifer sand columns. We coupled concentration breakthrough curve analysis with SIP monitoring and reactive transport modeling to relate spatiotemporal NP concentration distributions to geo-electrical signals. Changes in the real (σ') conductivity at three different locations along the columns closely correlated with model-computed total (solid plus aqueous phase) NP concentrations during the propagation of a NP slug. The imaginary conductivity (σ″) correlated closely with the arrival of the NP-slug. However, during the receding front, bimodal σ″-signal peak behaviour was observed propagating through the columns, indicating the existence of complex in situ NP transport dynamics, potentially revealing the rupture of nanoclusters upon straining and their effect on bulk charge storage that may not be obvious from breakthrough curve data alone. Fitting of a double Cole-Cole relaxation model yielded distinct shifts in relaxation time (τ) associated with the polarization of smaller length-scale particles. Post-NP pulse τ and σ″ did not return to pre-injection values; these lingering signals were caused by retained NP concentrations as low as 8.8 mg kg-1. Our results support the applicability of SIP for spatial and temporal monitoring of NP distributions, with implications for the investigation of NP transport and nanoremediation strategies.

Distribution and origin of potentially toxic elements in a multi-aquifer system.

Pollution of the potentially toxic elements (PTEs) is a major concern in the metal ore-mining environment. Active polymetallic industries and mines cause great continuous devastation of both terrestrial and aquatic environments on a local and regional scale. This study investigated the pollution of surface water and groundwater in the area containing six large-scale iron ore mines, which have been in operation for more than a few decades. In order to assess the PTEs pollution, the spatial and temporal distributions of 13 different PTEs (Al, As, Co, Li, Mn, Mo, Ni, Pb, Rb, Se, Si, Sr, and Zn) were measured in 42 water samples collected from the multi-aquifer system including three distinct aquifers (upper alluvial aquifer (UAA), lower alluvial aquifer (LAA), and hard-rock aquifer (HRA)) of the Gohar-Zamin mining area in Iran. The highest concentrations of total dissolved solids (TDS = 164,000 mg/l) and PTEs were measured in HRA. Three trends were identified between the PTE concentration and increasing of TDS based on Spearman correlation analysis: (1) an increasing trend for Al, Co, Li, Mn, Rb, Se, Sr, and Ni; there were strong positive correlations in HRA between TDS and Mn (0.83), Al (0.65), Co (0.74), Li (0.90), Ni (0.83), Rb (0.91), Se (0.82), and Sr (0.84), suggesting a common origin for these elements; (2) no obvious trend for As and Mo, no correlation was founded between As and Mo with other PTEs and TDS, indicating a natural geogenic origin and mutual dependencies of these elements; and (3) a decreasing trend for Si, Zn, and Pb; TDS had a significantly negative correlation with the PTEs and attributing to different chemical properties of infiltrated groundwater. In the principal component analysis (PCA), the first PC that covers 85.09% of the total observed variance is mainly attributed the groundwater salinization. This component is composed of Al, Co, Li, Mn, Rb, Se, Sr, and Ni. The second PC contains elements As and Mo. This PC explain 14.4% of total variance and may be referred to natural origin of PTEs. Si, Zn, and Pb are in the third principal component and cover 9.64% of the variance of the data. Third PC have been attributed to lithogenic and/or primary water chemistry factors. The PTE pollution were evaluated based on heavy metal evaluation index (HEI), heavy metal pollution index (HPI), and degree of contamination (Cd). The results indicated that all of the groundwater samples collected from HRA had HEI, HPI, and Cd values greater than 21, 264, and 14 (highly pollution limits of indices), respectively, and were classified as highly polluted groundwater. HPI values within the UAA, LAA, and salt playa (SP) were lower than the critical level of 100, suggesting a threshold for the drinking water pollution. Moreover, HEI and Cd with values of less than 10 and 7 suggested low-level pollution in UAA, LAA, and SP. However, the contaminated level of PTEs exceeded the WHO standard for drinking water in HRA only. Since groundwater in HRA is a brine with the high values of PTEs, pumping of this water out to the surrounding natural environment may cause harmful impacts on the environment and perhaps living species in Bahram-e-Goor protected area. Graphical abstract.

Phosphorus binding to soil organic matter via ternary complexes with calcium.

Soil organic matter (SOM) is known to exert a major control on the mobility and bioavailability of cationic nutrients. However, the role of SOM in the fate of anionic nutrients, especially phosphorus (P), is less well characterized. The objectives of this study were to (1) compare the formation of binary complexes of calcium (Ca) with humic acids (HA) extracted from two contrasting soils, and (2) determine if binary HA-Ca complexes could incorporate P by forming ternary HA-Ca-P complexes. The Ca binding capacities of the HA extracted from an agricultural organic soil (AOS) and a pristine riparian soil (RS) were measured via potentiometric titrations; the formation of ternary complexes was analyzed by size fractionation using MWCO tubes. Proton and Ca binding capacities of RS-HA were higher than AOS-HA, and pH had a weaker effect on Ca binding to RS-HA. These differences are consistent with lower proportions of aromatic groups, and a higher proportion of alkyl groups derived from 13C NMR spectroscopy. Together, the NMR, titration and MWCO data indicate that Ca binds to RS-HA through monodentate complexes and electrostatic attraction that are capable of binding P producing ternary complexes. In contrast, at pH 8.5 Ca forms bidentate complexes with AOS-HA, which do not provide bridging positions to incorporate P. Overall, our results imply that the formation of HA-Ca and HA-Ca-P complexes depend on the structure of the HA, and that complexation to HA may play an important role in the fate of P in terrestrial and aquatic environments.

Effects of dissolved organic phase composition and salinity on the engineered sulfate application in a flow-through system.

Engineered sulfate application has been proposed as an effective remedy to enhance the rate-limited biodegradation of petroleum-hydrocarbon-contaminated subsurface environments, but the effects of dissolved organic phase composition and salinity on the efficiency of this method are unknown. A series of flow-through experiments were conducted for 150 days and dissolved benzene, toluene, naphthalene, and 1-methylnaphthalene were injected under sulfate-reducing and three different salinity conditions for 80 pore volumes. Then, polycyclic aromatic hydrocarbons (PAHs) were omitted from the influent solution and just dissolved benzene and toluene were injected to investigate the influence of dissolved phase composition on treatment efficiency. A stronger sorption capacity for PAHs was observed and the retardation of the injected organic compounds followed the order of benzene < toluene < naphthalene < 1-methylnaphthalene. Mass balance analyses indicated that 50 and 15% of toluene and 1-methlynaphtalene were degraded, respectively. Around 5% of the injected naphthalene degraded after injecting > 60 PVs influent solution, and benzene slightly degraded following the removal of PAH compounds. The results showed substrate interactions and composition can result in rate-limited and insufficient biodegradation. Similar reducing conditions and organic utilization were observed for different salinity conditions in the presence of the multi-component dissolved organic phase. This was attributed to the dominant microbial community involved in toluene degradation that exerted catabolic repression on the simultaneous utilization of other organic compounds and were not susceptible to changes in salinity.

Transport, retention, and release of Escherichia coli and Rhodococcus erythropolis through dry natural soils as affected by water repellency.

Microbial transport in soil affects pathogen retention, colonization, and innoculant delivery in bioremediating agricultural soils. Various bacteria strains residing in the fluid phases of soils are potential contaminants affecting human health. We measured the transport of hydrophilic Escherichia coli (E. coli) and hydrophobic Rhodococcus erythropolis (R. erythropolis) bacteria through initially air-dried wettable or water-repellent soil columns to understand the effect of water repellency and the hydrophobicity of the organism on its retention, release, and transport properties. Bacteria suspensions infiltrated the top of the columns under saturated (0 cm) and unsaturated (-5 cm) flows in the air-dried (pulse 1) and rewetting (pulse 2) conditions. Cells were recovered from the leachates and the soil extracts by the viable counts. Wettable soil efficiently retained both hydrophobic and hydrophilic bacteria (>80%) in initial air-dried conditions (pulse 1). Even after rewetting, and the formation and expansion of water films and corresponding reduction of the air-water interfacial area (pulse 2), few bacteria were released (maximum 31.5% and 10.1% for saturated and unsaturated flows, respectively), whereas more cells were released from the water-repellent counterpart (more that 72%). The smaller size of hydrophobic R. erythropolis made cell transport possible within the thinner water films of both soils compared to hydrophilic E. coli through pulses 1 and 2. The shape of each strain's retention profiles was uniform and exponential as influenced by soil, strain, and water flow conditions. The results suggest that hydrophobic bacteria will disperse readily when leached into initially dry soil, while hydrophilic bacteria are more susceptible to leaching, posing a risk of pathogen contamination. Clearly the wettability of soil and organisms affects fate and transport.

Bioretention cells under cold climate conditions: Effects of freezing and thawing on water infiltration, soil structure, and nutrient removal.

Bioretention cells are a popular control strategy for stormwater volume and quality, but their efficiency for water infiltration and nutrient removal under cold climate conditions has been poorly studied. In this work, soil cores were collected from an active bioretention cell containing engineered soil material amended with a phosphate sorbent medium. The cores were used in laboratory column experiments conducted to obtain a detailed characterization of the soil's bioretention performance during six consecutive freeze-thaw cycles (FTCs, from -10 to +10 °C). At the start of each FTC, the experimental column undergoing the FTCs and a control column kept at room temperature were supplied with a solution containing 25 mg/L of bromide, nitrate and phosphate. Water saturated conditions were established to mimic the presence of an internal water storage zone to support anaerobic nitrate removal. At the end of each FTC, the pore solution was allowed to drain from the columns. The results indicate that the FTCs enhanced the infiltration efficiency of the soil: with each successive cycle the drainage rate increased in the experimental column. Freezing and thawing also increased the saturated hydraulic conductivity of the bioretention soil. X-ray tomography imaging identified a key role of macro-pore formation in maintaining high infiltration rates. Both aqueous nitrate and phosphate supplied to the columns were nearly completely removed from solution. Sufficiently long retention times and the presence of the internal water storage zone promoted anaerobic nitrate elimination despite the low temperatures. Dissolved phosphate was efficiently trapped at all depths in the soil columns, with ≤2% of the added stormwater phosphate recovered in the drainage effluent. These findings imply that, when designed properly, bioretention cells can support high infiltration rates and mitigate nutrient pollution in cold climates.

Sensing Coated Iron-Oxide Nanoparticles with Spectral Induced Polarization (SIP): Experiments in Natural Sand Packed Flow-Through Columns.

The development of nanoparticle-based soil remediation techniques is hindered by the lack of accurate in situ nanoparticle (NP) monitoring and characterization methods. Spectral induced polarization (SIP), a noninvasive geophysical technique, offers a promising approach to detect and quantify NPs in porous media. However, its successful implementation as a monitoring tool requires an understanding of the polarization mechanisms, the governing NP-associated SIP responses and their dependence on the stabilizing coatings that are typically used for NPs deployed in environmental applications. Herein, we present SIP responses (0.1-10 000 Hz) measured during injection of a poloxamer-coated superparamagnetic iron-oxide nanoparticle (SPION) suspension in flow-through columns packed with natural sand from the Borden aquifer. An advective-dispersive transport model is fitted to outflow SPION concentration measurements to compute average concentrations over the SIP spatial response domain (within the columns). The average SPION concentrations are compared with the real and imaginary components of the complex conductivity. Excellent correspondence is found between the average SPION concentrations in the columns and the imaginary conductivity values, suggesting that NP-mediated polarization (that is, charge storage) increases proportionally with increasing SPION concentration. Our results support the possibility of SIP monitoring of spatial and temporal NP distributions, which can be immediately deployed in bench-scale studies with the prospect of future real-world field applications.

Sorption of benzene and naphthalene on (semi)-arid coastal soil as a function of salinity and temperature.

Considerable activities from the oil and natural gas sector have risen some concerns about the pollution of soil and groundwater by petroleum hydrocarbons (PHCs) in (semi)-arid coastal regions. The understanding of the fate and transport of PHCs in these regions is therefore necessary to develop strategies for remediation. To quantify the sorption rates of PHCs in (semi)-arid coastal soil environments, we conducted a series of controlled-laboratory batch experiments under variable temperature and salinity conditions. The soil samples were collected from the eastern coast of Qatar which is near the two largest off-shore oil and natural gas fields of the country (North Gas and Al-Shaheen Oil Fields), and the volatile benzene and naphthalene were used as PHCs. The characterization of soil samples showed sand classification with the texture class of sabkha and saline beach sandy soils with calcite as potential dominant mineral. The concentrations of dissolved chloride and sodium were found to be high (> 400 mg L-1) with a chloride-to­sodium ratio of about 1.7. The results of sorption experiments showed that the rates of naphthalene sorption were more than for benzene, where the initial aqueous concentrations of benzene and naphthalene were reduced at equilibrium due to sorption by about 14-25% and 65-79%, respectively. This difference was attributed mainly to the organic carbon-water partitioning coefficient which is higher for naphthalene. The sorption rate experiments showed that sorption was stronger for benzene under higher salinity and lower temperature conditions. The sorption of naphthalene was not affected by the change in salinity but increased by 18% when the temperature decreased from 35 to 5 °C. A sorption kinetic model was also applied to define the sorption behavior of benzene and naphthalene for the coastal soil collected in Qatar and the best fits were achieved with the Langmuir sorption isotherm.

Benthic nitrite exchanges in the Seine River (France): An early diagenetic modeling analysis.

Nitrite is a toxic intermediate compound in the nitrogen (N) cycle. Elevated concentrations of nitrite have been observed in the Seine River, raising questions about its sources and fate. Here, we assess the role of bottom sediments as potential sources or sinks of nitrite along the river continuum. Sediment cores were collected from two depocenters, one located upstream, the other downstream, from the largest wastewater treatment plant (WWTP) servicing the conurbation of Paris. Pore water profiles of oxygen, nitrate, nitrite and ammonium were measured. Ammonium, nitrate and nitrite fluxes across the sediment-water interface (SWI) were determined in separate core incubation experiments. The data were interpreted with a one-dimensional, multi-component reactive transport model, which accounts for the production and consumption of nitrite through nitrification, denitrification, anammox and dissimilatory nitrate reduction to ammonium (DNRA). In all core incubation experiments, nitrate uptake by the sediments was observed, indicative of high rates of denitrification. In contrast, for both sampling locations, the sediments in cores collected in August 2012 acted as sinks for nitrite, but those collected in October 2013 released nitrite to the overlying water. The model results suggest that the first step of nitrification generated most pore water nitrite at the two locations. While nitrification was also the main pathway consuming nitrite in the sediments upstream of the WWTP, anammox dominated nitrite removal at the downstream site. Sensitivity analyses indicated that the magnitude and direction of the benthic nitrite fluxes most strongly depend on bottom water oxygenation and the deposition flux of labile organic matter.

Linking Spectral Induced Polarization (SIP) and Subsurface Microbial Processes: Results from Sand Column Incubation Experiments.

Geophysical techniques, such as spectral induced polarization (SIP), offer potentially powerful approaches for in situ monitoring of subsurface biogeochemistry. The successful implementation of these techniques as monitoring tools for reactive transport phenomena, however, requires the deconvolution of multiple contributions to measured signals. Here, we present SIP spectra and complementary biogeochemical data obtained in saturated columns packed with alternating layers of ferrihydrite-coated and pure quartz sand, and inoculated with Shewanella oneidensis supplemented with lactate and nitrate. A biomass-explicit diffusion-reaction model is fitted to the experimental biogeochemical data. Overall, the results highlight that (1) the temporal response of the measured imaginary conductivity peaks parallels the microbial growth and decay dynamics in the columns, and (2) SIP is sensitive to changes in microbial abundance and cell surface charging properties, even at relatively low cell densities (<108 cells mL-1). Relaxation times (τ) derived using the Cole-Cole model vary with the dominant electron accepting process, nitrate or ferric iron reduction. The observed range of τ values, 0.012-0.107 s, yields effective polarization diameters in the range 1-3 µm, that is, 2 orders of magnitude smaller than the smallest quartz grains in the columns, suggesting that polarization of the bacterial cells controls the observed chargeability and relaxation dynamics in the experiments.

The role of groundwater discharge fluxes on Si:P ratios in a major tributary to Lake Erie.

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.