The Significance of Precise Diabetes Diagnosis: A Case of Euglycemic Diabetic Ketoacidosis Induced by the Introduction of Empagliflozin with Simultaneous Reduction of Insulin Dosage.

Euglycemic diabetic ketoacidosis (euDKA) is a rare but severe metabolic complication of diabetes mellitus characterised by elevated anion gap metabolic acidosis despite normal or mildly elevated blood glucose levels. Sodium-glucose cotransporter 2 inhibitors (SGLT2i) have emerged as effective antidiabetic medications, yet their use is associated with an increased risk of euDKA, especially when coupled with insulin dose reduction. We present the case of a 50-year-old male with a 20-year history of diabetes mellitus, initially managed with insulin and metformin, who developed euDKA following the introduction of empagliflozin and sitagliptin alongside a reduction in insulin therapy. Despite normoglycaemia the patient exhibited symptoms of ketoacidosis, including chronic fatigue, polydipsia, and polyuria. Diagnostic workup revealed metabolic acidosis, elevated inflammatory markers, acute kidney injury and ketonuria. Subsequent specialised laboratory tests confirmed type 1 diabetes mellitus (T1DM) with the presence of anti-glutamic acid decarboxylase (anti-GAD) antibodies and the absence of C-peptide secretion. Management involved fluid therapy, intravenous insulin and glucose administration. This case underscores the diagnostic challenges of euDKA and emphasises the importance of differentiating between T1DM and T2DM, as management strategies vary significantly. Patient education on insulin therapy and injection techniques is crucial to prevent complications such as improper insulin delivery and dose reduction, which can precipitate euDKA. In conclusion, clinicians should be vigilant for euDKA in patients on SGLT2 inhibitors, particularly when insulin dose reduction is involved. Comprehensive patient education and accurate differentiation between diabetes types are essential for timely diagnosis and optimal management, thereby reducing the risk of severe complications. LEARNING POINTS: The reduction in insulin doses combined with the introduction of an SGLT2 inhibitor in a patient with type 1 diabetes may lead to the development of a dangerous health complication known as euglycemic diabetic ketoacidosis.In cases of diagnostic uncertainty regarding the differentiation of diabetes types, measuring the levels of C-peptide and anti-GAD antibodies can be helpful.Abnormal glycaemic results in a patient using insulin may result from improper administration. During follow-up visits, it is worthwhile to check the subcutaneous tissue for lipodystrophy and also remind the patient about the necessity of rotating insulin injection sites.

Iron nitride nanoparticles for rapid dechlorination of mixed chlorinated ethene contamination.

Sulfidation and, more recently, nitriding have been recognized as promising modifications to enhance the selectivity of nanoscale zero-valent iron (nZVI) particles for trichloroethene (TCE). Herein, we investigated the performance of iron nitride (FexN) nanoparticles in the removal of a broader range of chlorinated ethenes (CEs), including tetrachloroethene (PCE), cis-1,2-dichloroethene (cis-DCE), and their mixture with TCE, and compared it to the performance of sulfidated nZVI (S-nZVI) prepared from the same precursor nZVI. Two distinct types of iron nitride (FexN) nanoparticles, containing γ'-Fe4N and ε-Fe2-3N phases, exhibited substantially higher PCE and cis-DCE dechlorination rates compared to S-nZVI. A similar effect was observed with a CE mixture, which was completely dechlorinated by both types of FexN nanoparticles within 10 days, whereas S-nZVI was able to remove only about half of the amount, most of which being TCE. Density functional theory calculations further revealed that the cleavage of the first C-Cl bond was the rate-limiting step for all CEs dechlorinated on the γ'-Fe4N(001) surface, with the reaction barriers of PCE and cis-DCE being 29.9, and 40.8 kJ mol-1, respectively. FexN nanoparticles proved to be highly effective in the remediation of PCE, cis-DCE, and mixed CE contamination.

Effects of silver sulfide nanoparticles on the earthworm Eisenia andrei.

The massive production and use of silver nanoparticles (Ag NPs) have led to their increasing release into the environment. Even though the antimicrobial and cytotoxic effects of native nanoparticles have been well studied, the environmental impacts of transformation products such as silver sulfide nanoparticles (Ag2S NPs) have not been elucidated. In the present study, we assessed the toxicity of Ag2S NPs and silver nitrate (AgNO3), as a source of Ag, to the earthworm Eisenia andrei using a nominal concentration of 5 mg Ag kg-1 soil. We used the OECD guidelines to assess effects on weight loss and mortality for 14 days. After exposure, we also extracted the immune effector cells (coelomocytes) and conducted a battery of biomarker tests. To ensure the quality of the toxicological results, the structural changes of NPs during the experiment and the uptake of silver by the earthworms were monitored. During the experiment, mortality effects were not detected, but a weight loss was observed in the earthworms exposed to Ag2S NPs. Altough Ag2S NPs were engulfed by E. andrei cells, neither phenoloxidase activity nor lipid peroxidation differed from the untreated control group. Cells from earthworms treated with Ag2S NPs exerted very broad value range of nitric oxide (NO) generation, suggesting an imbalance in the NO metabolism. Overall, this study suggests minimal risks associated with Ag2S NPs exposure to earthworms. However, further studies are needed to assure no immunotoxicological or chronic effects on a wider range of terrestrial organisms.

Iron Nitride Nanoparticles for Enhanced Reductive Dechlorination of Trichloroethylene.

Nitriding has been used for decades to improve the corrosion resistance of iron and steel materials. Moreover, iron nitrides (FexN) have been shown to give an outstanding catalytic performance in a wide range of applications. We demonstrate that nitriding also substantially enhances the reactivity of zerovalent iron nanoparticles (nZVI) used for groundwater remediation, alongside reducing particle corrosion. Two different types of FexN nanoparticles were synthesized by passing gaseous NH3/N2 mixtures over pristine nZVI at elevated temperatures. The resulting particles were composed mostly of face-centered cubic (γ'-Fe4N) and hexagonal close-packed (ε-Fe2-3N) arrangements. Nitriding was found to increase the particles' water contact angle and surface availability of iron in reduced forms. The two types of FexN nanoparticles showed a 20- and 5-fold increase in the trichloroethylene (TCE) dechlorination rate, compared to pristine nZVI, and about a 3-fold reduction in the hydrogen evolution rate. This was related to a low energy barrier of 27.0 kJ mol-1 for the first dechlorination step of TCE on the γ'-Fe4N(001) surface, as revealed by density functional theory calculations with an implicit solvation model. TCE dechlorination experiments with aged particles showed that the γ'-Fe4N nanoparticles retained high reactivity even after three months of aging. This combined theoretical-experimental study shows that FexN nanoparticles represent a new and potentially important tool for TCE dechlorination.

Discovering the potential of an nZVI-biochar composite as a material for the nanobioremediation of chlorinated solvents in groundwater: Degradation efficiency and effect on resident microorganisms.

Abiotic and biotic remediation of chlorinated ethenes (CEs) in groundwater from a real contaminated site was studied using biochar-based composites containing nanoscale zero-valent iron (nZVI/BC) and natural resident microbes/specific CE degraders supported by a whey addition. The material represented by the biochar matrix decorated by isolated iron nanoparticles or their aggregates, along with the added whey, was capable of a stepwise dechlorination of CEs. The tested materials (nZVI/BC and BC) were able to decrease the original TCE concentration by 99% in 30 days. Nevertheless, regarding the transformation products, it was clear that biotic as well as abiotic transformation mechanisms were involved in the transformation process when nonchlorinated volatiles (i.e., methane, ethane, ethene, and acetylene) were detected after the application of nZVI/BC and nZVI/BC with whey. The whey addition caused a massive increase in bacterial biomass in the groundwater samples (monitored by 16S rRNA sequencing and qPCR) that corresponded with the transformation of trichloro- and dichloro-CEs, and this process was accompanied by the formation of less chlorinated products. Moreover, the biostimulation step also eliminated the adverse effect caused by nZVI/BC (decrease in microbial biomass after nZVI/BC addition). The nZVI/BC material or its aging products, and probably together with vinyl chloride-respiring bacteria, were able to continue the further reductive dechlorination of dichlorinated CEs into nonhalogenated volatiles. Overall, the results of the present study demonstrate the potential, feasibility, and environmental safety of this nanobioremediation approach.

Effect of Copresence of Zerovalent Iron and Sulfate Reducing Bacteria on Reductive Dechlorination of Trichloroethylene.

Sulfur amendment of zerovalent iron (ZVI) materials has been shown to improve the reactivity and selectivity of ZVI toward a select group of organohalide contaminants in groundwater, most notably trichloroethene (TCE). In previous studies, chemical or mechanochemical sulfidation methods were used; however, the potential of using sulfate-reducing bacteria (SRB) to enable sulfur amendment has not been closely examined. In this study, lab-synthesized nanoscale ZVI (nZVI) and Peerless iron particles (ZVIPLS) were treated in a sulfate-reducing monoculture (D. desulfuricans) and an enrichment culture derived from freshwater sediments (AMR-1) prior to reactivity assessments with TCE as the model contaminant. ZVI conditioned in both cultures exhibited higher dechlorination efficiencies compared to unamended ZVIs. Remarkably, nZVI and ZVIPLS exposed to AMR-1 attained similar TCE dechlorination rates as their counterparts receiving chemical sulfidation (i.e., S-nZVI) using previously reported method. Product distribution data show that, in the SRB-ZVI system, abiotic dechlorination is the dominant TCE reduction pathway. In addition to dissolved sulfide, biogenic or synthesized FeS particles can enhance nZVI reactivity even as nZVI and FeS were not in direct contact, implying that SRB may influence the reactivity of ZVI via multiple mechanisms in different remediation situations. A shift in Archaea abundance in AMR-1 with nZVI amendment was observed but not with ZVIPLS. Overall, the synergy exhibited in the SRB-ZVI system may offer a valuable remediation strategy to overcome limitations of standalone biological or abiotic dechlorination approaches for chlorinated solvent abatement.

Carboxylated Graphene for Radical-Assisted Ultra-Trace-Level Water Treatment and Noble Metal Recovery.

Sorption technologies, enabling removal of heavy metals, play a pivotal role in meeting the global demands for unrestricted access to drinking water. Standard sorption technologies suffer from limited efficiency related to the weak sorbent-metal interaction. Further challenges include the development of technologies enabling smart metal recovery and sorbent regeneration. To this end, a densely functionalized graphene, with 33% by mass content of carboxyl groups, linked through direct C-C bonds (graphene acid, GA) represents a previously unexplored solution to this challenge. GA revealed excellent efficiency for removal of highly toxic metals, such as Cd2+ and Pb2+. Due to its selective chemistry, GA can bind heavy metals with high affinity, even at concentrations of 1 mg L-1 and in the presence of competing ions of natural drinking water, and reduce them down to drinking water allowance levels of a few µg L-1. This is not only due to carboxyl groups but also due to the stable radical centers of the GA structure, enabling metal ion-radical interactions, as proved by EPR, XPS, and density functional theory calculations. GA offers full structural integrity during the highly acidic and basic treatment, which is exploited for noble metal recovery (Ga3+, In3+, Pd2+) and sorbent regeneration. Owing to these attributes, GA represents a fully reusable metal sorbent, applicable also in electrochemical energy technologies, as illustrated with a GA/Pt catalyst derived from Pt4+-contaminated water.

Effervescent ferrate(VI)-based tablets as an effective means for removal SARS-CoV-2 RNA, pharmaceuticals and resistant bacteria from wastewater.

Waterborne pathogens including viruses, bacteria and micropollutants secreted from population can spread through the sewerage system. In this study, the efficiency of unique effervescent ferrate-based tablets was evaluated for total RNA and DNA removal, disinfection and degradation of micropollutants in hospital wastewater. For the purpose of testing, proposed tablets (based on citric acid or sodium dihydrogen phosphate) were used for various types of hospital wastewater with specific biological and chemical contamination. Total RNA destruction efficiency using tablets was 70-100% depending on the type of acidic component. DNA destruction efficiency was lower on the level 51-94% depending on the type of acidic component. In addition, our study confirms that effervescent ferrate-based tablets are able to efficiently remove of SARS-CoV-2 RNA from wastewater. Degradation of often detected micropollutants (antiepileptic, antidepressant, antihistamine, hypertensive and their metabolites) was dependent on the type of detected pharmaceuticals and on the acidic component used. Sodium dihydrogen phosphate based tablet appeared to be more effective than citric acid based tablet and removed some pharmaceuticals with efficiency higher than 97%. Last but not least, the disinfection ability was also verified. Tableted ferrates were confirmed to be an effective disinfectant and no resistant microorganisms were observed after treatment. Total and antibiotic resistant bacteria (coliforms and enterococci) were determined by cultivation on diagnostic selective agar growth media.

Sulfidated nano-scale zerovalent iron is able to effectively reduce in situ hexavalent chromium in a contaminated aquifer.

In a number of laboratory studies, sulfidated nanoscale zero-valent iron (S-nZVI) particles showed increased reactivity, reducing capacity, and electron selectivity for Cr(VI) removal from contaminated waters. In our study, core-shell S-nZVI particles were successfully injected into an aquifer contaminated with Cr(VI) at a former chrome plating facility. S-nZVI migrated towards monitoring wells, resulting in a rapid decrease in Cr(VI) and Crtot concentrations and a long-term decrease in groundwater redox potential observed even 35 m downstream the nearest injection well. Characterization of materials recovered from the injection and monitoring wells confirmed the presence of nZVI particles, together with iron corrosion products. Chromium was identified on the surface of the recovered iron particles as Cr(III), and its occurrence was linked to the formation of insoluble chromium-iron (oxyhydr)oxides such as CrxFe(1-x)(OH)3(s). Injected S-nZVI particles formed aggregates, which were slowly transformed into iron (oxyhydr)oxides and carbonate green rust. Elevated contents of Fe0 were detected even several months after injection, indicating good S-nZVI longevity. The sulfide shell was gradually disintegrated and/or dissolved. Geochemical modelling confirmed the overall stability of the resulting Cr(III) phase at field conditions. This study demonstrates the applicability of S-nZVI for the remediation of a Cr(VI)-contaminated aquifer.

Core-Shell Fe/FeS Nanoparticles with Controlled Shell Thickness for Enhanced Trichloroethylene Removal.

Zero-valent iron nanoparticles (nZVI) treated by reduced sulfur compounds (i.e., sulfidated nZVI, S-nZVI) have attracted increased attention as promising materials for environmental remediation. While the preparation of S-nZVI and its reactions with various groundwater contaminants such as trichloroethylene (TCE) were already a subject of several studies, nanoparticle synthesis procedures investigated so far were suited mainly for laboratory-scale preparation with only a limited possibility of easy and cost-effective large-scale production and FeS shell property control. This study presents a novel approach for synthesizing S-nZVI using commercially available nZVI particles that are treated with sodium sulfide in a concentrated slurry. This leads to S-nZVI particles that do not contain hazardous boron residues and can be easily prepared off-site. The resulting S-nZVI exhibits a core-shell structure where zero-valent iron is the dominant phase in the core, while the shell contains mostly amorphous iron sulfides. The average FeS shell thickness can be controlled by the applied sulfide concentration. Up to a 12-fold increase in the TCE removal and a 7-fold increase in the electron efficiency were observed upon amending nZVI with sulfide. Although the FeS shell thickness correlated with surface-area-normalized TCE removal rates, sulfidation negatively impacted the particle surface area, resulting in an optimal FeS shell thickness of approximately 7.3 nm. This corresponded to a particle S/Fe mass ratio of 0.0195. At all sulfide doses, the TCE degradation products were only fully dechlorinated hydrocarbons. Moreover, a nearly 100% chlorine balance was found at the end of the experiments, further confirming complete TCE degradation and the absence of chlorinated transformation products. The newly synthesized S-nZVI particles thus represent a promising remedial agent applicable at sites contaminated with TCE.

Smart synthetic maghemite nanoparticles with unique surface properties encode binding specificity toward AsIII.

Pristine ɣ-Fe2O3 nanoparticles, called surface active maghemite nanoparticles (SAMNs) display unprecedented colloidal stability and specific binding properties. Herein, the interactions of SAMNs with AsV and AsIII as surface molecular probes were comparatively studied. Thermodynamic and kinetic characterizations, along with chemical and structural analysis of SAMN@As complexes, evidenced two distinct binding modalities. Arsenite, emerged as an elective and specific ligand for SAMNs, whereas arsenate adsorption was more labile, pH dependent and ruled by different binding possibilities. In particular, AsIII oxyacid exclusively interacts through inner-sphere coordination occupying available surface crystal positions resembling a key-lock fitting, while AsV leads to both outer-sphere and inner-sphere complexes. Noteworthy, discrimination between AsV and AsIII was never reported for nanostructured maghemite evidencing the importance of synthetic route on surface properties of the nanomaterial. The present report, besides enriching the chemistry of nanosized iron oxides, suggests SAMNs application for the remediation of water contaminated by AsIII, the most threatening As species in water.

Sustainable Synthesis of Nanoscale Zerovalent Iron Particles for Environmental Remediation.

Nanoscale zerovalent iron (nZVI) particles represent an important material for diverse environmental applications because of their exceptional electron-donating properties, which can be exploited for applications such as reduction, catalysis, adsorption, and degradation of a broad range of pollutants. The synthesis and assembly of nZVI by using biological and natural sustainable resources is an attractive option for alleviating environmental contamination worldwide. In this Review, various green synthesis pathways for generating nZVI particles are summarized and compared with conventional chemical and physical methods. In addition to describing the latest environmentally benign methods for the synthesis of nZVI, their properties and interactions with diverse biomolecules are discussed, especially in the context of environmental remediation and catalysis. Future prospects in the field are also considered.

Oxidative stress in microbes after exposure to iron nanoparticles: analysis of aldehydes as oxidative damage products of lipids and proteins.

Due to their enhanced reactivity, metal and metal-oxide nanoscale zero-valent iron (nZVI) nanomaterials have been introduced into remediation practice. To ensure that environmental applications of nanomaterials are safe, their possible toxic effects should be described. However, there is still a lack of suitable toxicity tests that address the specific mode of action of nanoparticles, especially for nZVI. This contribution presents a novel approach for monitoring one of the most discussed adverse effects of nanoparticles, i.e., oxidative stress (OS). We optimized and developed an assay based on headspace-SPME-GC-MS analysis that enables the direct determination of volatile oxidative damage products (aldehydes) of lipids and proteins in microbial cultures after exposure to commercial types of nZVI. The method employs PDMS/DVB SPME fibers and pentafluorobenzyl derivatization, and the protocol was successfully tested using representatives of bacteria, fungi, and algae. Six aldehydes, namely, formaldehyde, acrolein, methional, benzaldehyde, glyoxal, and methylglyoxal, were detected in the cultures, and all of them exhibited dose-dependent sigmoidal responses. The presence of methional, which was detected in all cultures except those including an algal strain, documents that nZVI also caused oxidative damage to proteins in addition to lipids. The most sensitive toward nZVI exposure in terms of aldehyde production was the yeast strain Saccharomyces cerevisiae, which had an EC50 value of 0.08 g/L nZVI. To the best of our knowledge, this paper is the first to document the production of aldehydes resulting from lipids and proteins as a result of OS in microorganisms from different kingdoms after exposure to iron nanoparticles.

Hospital wastewaters treatment: Fenton reaction vs. BDDE vs. ferrate(VI).

Various types of micropollutants, e.g., pharmaceuticals and their metabolites and resistant strains of pathogenic microorganisms, are usually found in hospital wastewaters. The aim of this paper was to study the presence of 74 frequently used pharmaceuticals, legal and illegal drugs, and antibiotic-resistant bacteria in 5 hospital wastewaters in Slovakia and Czechia and to compare the efficiency of several advanced oxidations processes (AOPs) for sanitation and treatment of such highly polluted wastewaters. The occurrence of micropollutants and antibiotic-resistant bacteria was investigated by in-line SPE-LC-MS/MS technique and cultivation on antibiotic and antibiotic-free selective diagnostic media, respectively. The highest maximum concentrations were found for cotinine (6700 ng/L), bisoprolol (5200 ng/L), metoprolol (2600 ng/L), tramadol (2400 ng/L), sulfamethoxazole (1500 ng/L), and ranitidine (1400 ng/L). In the second part of the study, different advanced oxidation processes, modified Fenton reaction, ferrate(VI), and oxidation by boron-doped diamond electrode were tested in order to eliminate the abovementioned pollutants. Obtained results indicate that the modified Fenton reaction and application of boron-doped diamond electrode were able to eliminate almost the whole spectrum of selected micropollutants with efficiency higher than 90%. All studied methods achieved complete removal of the antibiotic-resistant bacteria present in hospital wastewaters.

Surface termination of MgB2 unveiled by a combination of adsorption experiments and theoretical calculations.

Superconductivity in polycrystalline and thin-film MgB2 is strongly affected by the termination of its surface, but a reliable determination of the surface termination is still a challenging task of surface chemistry. Here, the surface properties of superconducting MgB2 were investigated using a combination of inverse gas chromatography and van der Waals corrected density functional theory calculations. The dispersive surface energy was measured as a function of the surface coverage and its value (58 mJ m-2 to 48 mJ m-2) was verified by high-level non-local EXX + RPA calculations, which predicted that the dispersive contribution to the cleavage energy was 56 mJ m-2. The isosteric adsorption enthalpies of cyclohexane, dioxane, acetone and acetonitrile molecules were measured on an MgB2 sample and compared to the DFT calculated enthalpies for the Mg-terminated MgB2, B-terminated MgB2 and MgO(001) surfaces. The close agreement between theory and experiment for the Mg-terminated surface suggested that the magnesium termination is the dominant surface phase of MgB2. Thus, combining inverse gas chromatography experiments with theoretical calculations may provide information about the surface termination.

Electric-field enhanced reactivity and migration of iron nanoparticles with implications for groundwater treatment technologies: Proof of concept.

The extensive use of nanoscale zero-valent iron (nZVI) particles for groundwater treatment has been limited, in part, because of their non-selective reactivity and low mobility in aquatic environments. Herein, we describe and explore progressive changes in the reactivity and migration of aqueous dispersed nZVI particles under an applied DC electric field. Due to the applied electric field with an intensity of about 1 V cm-1, the solution oxidation-reduction potential (ORP) remained as low as -200 mV for at least 32 days, which was in agreement with the persistence of the reduced iron species (mainly Fe(II)), and led to substantially prolonged reactivity of the original nZVI. The treatment of chlorinated ethenes (DCE > PCE > TCE) was markedly faster, individual CHC compounds were eliminated with the same kinetics and no lesser-chlorinated intermediates were accumulated, following thus the direct dechlorination scheme. When nZVI-dispersion flows towards the anode through vertical laboratory columns filled with quartz sand, significant enhancement of nZVI migration was recorded because of lower extent of nanoparticle aggregation and increased repulsion forces between the nanoparticles and the surface of silica dioxide. The results of this study have significant consequences for groundwater remediation, mainly for the treatment of slowly degradable DCE in real CHC contaminated groundwater, where it could improve the reactivity, the longevity and the migration of nZVI particles.

Novel assay for the toxicity evaluation of nanoscale zero-valent iron and derived nanomaterials based on lipid peroxidation in bacterial species.

Nano-scale zero-valent iron (nZVI) began attracting research attention in remediation practice in recent decades as a prospective nanomaterial applicable to various contaminated matrices. Despite concerns about the negative effects of nanomaterials on ecosystems, the number of reliable toxicity tests is limited. We have developed a test based on the evaluation of oxidative stress (OS). The test employed the analysis of a typical OS marker (malondialdehyde, MDA), after exposure of six bacterial strains to the tested nanomaterial. We also attempted to use other OS and cell membrane damage assays, including the determination of glutathione and lactate dehydrogenase, respectively. However, we found that the components of these assays interfered with nZVI; therefore, these tests were not applicable. The MDA assay was tested using nZVI and three newly engineered oxide shell nZVI materials with different oxide thicknesses. Six different bacterial species were employed, and the results showed that the test was fully applicable for the concentrations of nanomaterials used in remediation practice (0.1-10 g/L). MDA was produced in a dose-response manner, and the bacteria showed a similar response toward pure pyrophoric nZVI, reaching EC50 values of 0.3-1.1 g/L. We observed different responses in the absolute production of MDA; however, the MDA concentrations were correlated with the cell membrane surfaces of the individual strains (R > 0.75; P < 0.09). Additionally, the EC50 values correlated with the thickness of the oxide shells (except for Escherichia coli: R > 0.95; P < 0.05), documenting the reliability of the assay, where reactivity was confirmed to be an important factor for reactive oxygen species production.

The impact of wetland on neutral mine drainage from mining wastes at Luanshya in the Zambian Copperbelt in the framework of climate change.

The impact of a natural wetland ("dambo" in Zambia) on neutral mine drainage at Luanshya in the Zambian Copperbelt has been investigated during an intermediate discharge period (July) using a multi-method characterization of solid phase samples, sequential extraction analysis, X-ray diffraction, Mössbauer spectroscopy, and scanning electron microscopy combined with water analyses, isotopic analyses, and geochemical modeling. In the wetland, the principal identified solid phases in sediments were carbonates, gypsum, and ferric oxyhydroxides. A significant portion of the ochres was present as insoluble hematite. Mine drainage pH values decrease, and log [Formula: see text] values increase after inflow of water into the wetland; dissolved and suspended concentrations of Fe, Mn, Cu, and Co also decrease. Based on speciation calculations, there is no precipitation of secondary Cu and Co minerals in the period of sampling, but it can occur later in dry period when the flow rate is reduced. Concentrations of sulfate decrease, and values of δ34S(SO4) in the wetland increase in parallel, suggesting sulfate reduction is occurring. In more advanced dry period, the discharge in mine drainage stream is probably much lower and water can reach supersaturation with respect to minerals such as gypsum, which has been found in sediments. Wetlands have a positive impact on mine drainage water quality due to the removal of metals by adsorption, co-precipitation, and filtration of colloids. However, there can also be a rebound of contamination by seepage inflow downstream from the wetland. Ongoing climate change with extreme hydrologic events may enhance differences between dry and rainy seasons with resulting faster mobilization of contaminants.

Removal of arsenate and antimonate by acid-treated Fe-rich clays.

Iron impurities in clays degrade the quality in many aspects, but available Fe oxides can significantly improve adsorption affinity of clays to anionic particles. Two natural Fe-rich clays (kaolin and bentonite) were treated in 0.5 M HCl (pH = 1.1) and 0.15 M (COOH)2 (pH = 1.2), and then used to adsorb AsV/SbV oxyanions from model solutions. After acid leaching, the equilibrium sorption capacities (qmax) increased from 2.3 × 10-3 to 39.2 × 10-3 mmol g-1 for AsV and from 2.4 × 10-3 to 40.1 × 10-3 mmol g-1 for SbV, more than doubling the adsorption yields (≈95%) of both oxyanions. Leaching in 0.5 M HCl enhanced both AsV and SbV adsorption, whereas leaching in 0.15 M (COOH)2 mainly improved the adsorption of SbV. Bentonite, which contained fewer crystalline forms of Fe, exhibited better sorption properties for both oxyanions. The leaching of Fe followed first-order kinetics, whereas the adsorption of AsV/SbV followed second-order kinetics. Acid leaching of Fe-rich clays can be used for the preparation of highly selective anionactive sorbents.

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H2O2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.