Competitive Adsorption of Cd(II), Cr(VI), and Pb(II) onto Nanomaghemite: A Spectroscopic and Modeling Approach

A combined modeling and spectroscopic approach is used to describe Cd­(II), Cr­(VI), and Pb­(II) adsorption onto nanomaghemite and nanomaghemite coated quartz. A pseudo-second order kinetic model fitted the adsorption data well. The sorption capacity of nanomaghemite was evaluated using a Langmuir isotherm model, and a diffuse double layer surface complexation model (DLM) was developed to describe metal adsorption. Adsorption mechanisms were assessed using X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. Pb­(II) adsorption occurs mainly via formation of inner-sphere complexes, whereas Cr­(VI) likely adsorbs mainly as outer-sphere complexes and Cd­(II) as a mixture of inner- and outer-sphere complexes. The simple DLM describes well the pH-dependence of single adsorption edges. However, it fails to adequately capture metal adsorption behavior over broad ranges of ionic strength or metal-loading on the sorbents. For systems with equimolar concentrations of Pb­(II), Cd­(II), and Cr­(VI). Pb­(II) adsorption was reasonably well predicted by the DLM, but predictions were poorer for Cr­(VI) and Cd­(II). This study demonstrates that a simple DLM can describe well the adsorption of the studied metals in mixed sorbate–sorbent systems, but only under narrow ranges of ionic strength or metal loading. The results also highlight the sorption potential of nanomaghemite for metals in complex systems

Sublethal and Reproductive Effects of Acute and Chronic Exposure to Flowback and Produced Water from Hydraulic Fracturing on the Water Flea <i>Daphnia magna</i>

Hydraulic fracturing is an industrial process allowing for the extraction of gas or oil. To fracture the rocks, a proprietary mix of chemicals is injected under high pressure, which later returns to the surface as flowback and produced water (FPW). FPW is a complex chemical mixture consisting of trace metals, organic compounds, and often, high levels of salts. FPW toxicity to the model freshwater crustacean <i>Daphnia magna</i> was characterized utilizing acute (48 h median lethal concentrations; LC₅₀) and chronic (21 day) exposures. A decrease in reproduction was observed, with a mean value of 18.5 neonates produced per replicate over a 21 day chronic exposure to 0.04% FPW, which was a significant decrease from the average of 64 neonates produced in the controls. The time to first brood was delayed in the highest FPW (0.04%) treatment. Neonates exhibited an LC₅₀ of 0.19% of full-strength FPW, making them more sensitive than adults, which displayed an LC₅₀ value of 0.75%. Quantitative PCR highlighted significant changes in expression of genes encoding xenobiotic metabolism (<i>cyp4</i>) and moulting (<i>cut</i>). This study is the first to characterize chronic FPW toxicity and will help with the development of environmental monitoring and risk assessment of FPW spills

Thermodynamic Analysis of Nickel(II) and Zinc(II) Adsorption to Biochar

While numerous studies have investigated metal uptake from solution by biochar, few of these have developed a mechanistic understanding of the adsorption reactions that occur at the biochar surface. In this study, we explore a combined modeling and spectroscopic approach for the first time to describe the molecular level adsorption of Ni­(II) and Zn­(II) to five types of biochar. Following thorough characterization, potentiometric titrations were carried out to measure the proton (H⁺) reactivity of each biochar, and the data was used to develop protonation models. Surface complexation modeling (SCM) supported by synchrotron-based extended X-ray absorption fine structure (EXAFS) was then used to gain insights into the molecular scale metal–biochar surface reactions. The SCM approach was combined with isothermal titration calorimetry (ITC) data to determine the thermodynamic driving forces of metal adsorption. Our results show that the reactivity of biochar toward Ni­(II) and Zn­(II) directly relates to the site densities of biochar. EXAFS along with FT-IR analyses, suggest that Ni­(II) and Zn­(II) adsorption occurred primarily through proton-active carboxyl (−COOH) and hydroxyl (−OH) functional groups on the biochar surface. SCM-ITC analyses revealed that the enthalpies of protonation are exothermic and Ni­(II) and Zn­(II) complexes with biochar surface are slightly exothermic to slightly endothermic. The results obtained from these combined approaches contribute to the better understanding of molecular scale metal adsorption onto the biochar surface, and will facilitate the further development of thermodynamics-based, predictive approaches to biochar removal of metals from contaminated water

Linking Topographical Ring Features to Geochemical and Geophysical Anomalies

Circular features in forests seen from air have been studied for several decades at different locations around the world. Forest rings, as they are called in Canada’s boreal forests, express several geochemical (pH, carbonate content) and geophysical (surface potential) anomalies on their 20–30 m wide ring edges. Although it has been proposed that microbial processes may cause these anomalies, the exact mechanisms of ring formation are still unknown. We focused on the Thorn North forest ring in Ontario, Canada to correlate the surface potential anomaly to soil gas concentrations. Field measurements showed that the surface potential drop at the ring edge center is framed by peaks in CO2 production, which is linked to O2 depletion and methane generation. Carbon isotope signatures were found to drop to lighter values (down to −20‰), suggesting increased respiration. Higher concentrations of uronic acids bound to extracellular polymeric substances were found, indicating that the surface potential anomaly is linked to respiration. 16S rRNA gene sequencing of shallow soil did not indicate a dominant microbial group on the edges; instead, principal component analysis showed that the microbial composition was controlled by the substrate (clayey vs. sandy soil), therefore future studies should focus on deeper ground layers.</p

Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant

Reducing Conditions Influence U(IV) Accumulation in Sediments during <i>In Situ</i> Bioremediation

This study presents field experiments conducted in a contaminated aquifer in Rifle, CO, to determine the speciation and accumulation of uranium in sediments during in situ bioreduction. We applied synchrotron-based X-ray spectroscopy and imaging techniques as well as aqueous chemistry measurements to identify changes in U speciation in water and sediment in the first days follwing electron donor amendment. Limited changes in U solid speciation were observed throughout the duration of this study, and non-crystalline U(IV) was identified in all samples obtained. However, U accumulation rates strongly increased during in situ bioreduction, when the dominant microbial regime transitioned from iron- to sulfate-reducing conditions. Results suggest that uranium is enzymatically reduced during Fe reduction, as expected. Mineral grain coatings newly formed during sulfate reduction act as reduction hotspots, where numerous reductants can act as electron donors [Fe(II), S(II), and microbial extracellular polymeric substances] that bind and reduce U. The results have implications for identifying how changes in the dominant reducing mechanism, such as Fe versus sulfate reduction, affect trace metal speciation and accumulation. The outcomes from this study provide additional insights into uranium accumulation mechanisms in sediments that could be useful for the refinement of quantitative models describing redox processes and contaminant dynamics in floodplain aquifers

Persisting Effects in <i>Daphnia magna</i> Following an Acute Exposure to Flowback and Produced Waters from the Montney Formation

Hydraulic fracturing extracts oil and gas through the injection of water and proppants into subterranean formations. These injected fluids mix with the host rock formation and return to the surface as a complex wastewater containing salts, metals, and organic compounds, termed flowback and produced water (FPW). Previous research indicates that FPW is toxic to Daphnia magna (D. magna), impairing reproduction, molting, and maturation time; however, recovery from FPW has not been extensively studied. Species unable to recover have drastic impacts on populations on the ecological scale; thus, this study sought to understand if recovery from an acute 48 h FPW exposure was possible in the freshwater invertebrate, D. magna by using a combination of physiological and molecular analyses. FPW (0.75%) reduced reproduction by 30% and survivorship to 32% compared to controls. System-level quantitative proteomic analyses demonstrate extensive perturbation of metabolism and protein transport in both 0.25 and 0.75% FPW treatments after a 48 h FPW exposure. Collectively, our data indicate that D. magna are unable to recover from acute 48 h exposures to ≥0.25% FPW, as evidence of toxicity persists for at least 19 days post-exposure. This study highlights the importance of considering persisting effects following FPW remediation when modeling potential spill scenarios

Field- and Lab-Based Potentiometric Titrations of Microbial Mats from the Fairmont Hot Spring, Canada

<p>Potentiometric titrations are an effective tool to constrain the protonation constants and site concentrations for microbial surface ligands. Protonation models developed from these experiments are often coupled with data from metal adsorption experiments to calculate microbial ligand-metal binding constants. Ultimately, the resulting surface complexation models can be used to predict metal immobilization behavior across diverse chemical conditions. However, most protonation and metal-ligand thermodynamic constants have been generated in laboratory experiments that use cultured microbes which may differ in their chemical reactivity from environmental samples. In this study, we investigate the use of <i>in situ</i> field potentiometric titrations of microbial mats at a carbonate hot spring located at Fairmont Hot Springs, British Columbia, with the aim to study microbial reactivities in a natural field system. We found that authigenic carbonate minerals complicated the potentiometric titration process due to a “carbonate spike” introduced by the contribution of inorganic carbonate mineral dissolution and subsequent carbonate speciation changes during the transition from low to high pH. This inhibits the determination of microbial surface ligand variety and concentrations. Our preliminary study also highlights the need for developing novel probes to quantify <i>in situ</i> microbial mat reactivity in future field investigations.</p