Iron-based materials used in water treatment and groundwater remediation—especially micro- and nanosized zerovalent iron (nZVI)—can be more effective when modified with lower-valent forms of sulfur (i.e., “sulfidated”). Controlled sulfidation for this purpose (using sulfide, dithionite, etc.) is the main topic of this review, but insights are derived by comparison with related and comparatively well-characterized processes such as corrosion of iron in sulfidic waters and abiotic natural attenuation by iron sulfide minerals. Material characterization shows that varying sulfidation protocols (e.g., concerted or sequential) and key operational variables (e.g., S/Fe ratio and sulfidation duration) result in materials with structures and morphologies ranging from core–shell to multiphase. A meta-analysis of available kinetic data for dechlorination under anoxic conditions, shows that sulfidation usually increases dechlorination rates, and simultaneously hydrogen production is suppressed. Therefore, sulfidation can greatly improve the efficiency of utilization of reducing equivalents for contaminant removal. This benefit is most likely due to inhibited corrosion as a result of sulfidation. Sulfidation may also favor desirable pathways of contaminant removal, such as (i) dechlorination by reductive elimination rather than hydrogenolysis and (ii) sequestration of metals as sulfides that could be resistant to reoxidation. Under oxic conditions, sulfidation is shown to enhance heterogeneous catalytic oxidation of contaminants. These net effects of sulfidation on contaminant removal by iron-based materials may substantially improve their practical utility for water treatment and remediation of contaminated groundwater.

The synthesis, stability, and toxicity of engineered metal nanoparticles (ENPs) have been extensively studied during the past two decades. In contrast, research on the formation, fate, and ecological effects of naturally-occurring nanoparticles (NNPs) has become a focus of attention only recently. The natural existence of metal nanoparticles and their oxides/sulfides in waters, wastewaters, ore deposits, mining regions, and hydrothermal vents, as exemplified by the formation of nanoparticles containing silver and gold (AgNPs and AuNPs), Fe, Mn, pyrite (FeS₂), Ag₂S, CuS, CdS, and ZnS, is dictated largely by environmental conditions (temperature, pH, oxic/anoxic, light, and concentration and characteristics of natural organic matter (NOM)). Examples include the formation of nanoparticles containing pyrite, Cu and Zn-containing pyrite, and iron in hydrothermal vent black smoker emissions. Metal sulfide nanoparticles can be formed directly from their precursor ions or indirectly by sulfide ion-assisted transformation of the corresponding metal oxides under anaerobic conditions. This tutorial focuses on the formation mechanisms, fate, and toxicity of natural metal nanoparticles. Natural waters containing Ag(I) and Au(III) ions in the presence of NOM generate AgNPs and AuNPs under thermal, non-thermal, and photochemical conditions. These processes are significantly accelerated by existing redox species of iron (Fe(II)/Fe(III)). NOM, metal–NOM complexes, and reactive oxygen species (ROS) such as O₂˙⁻, ˙OH, and H₂O₂ are largely responsible for the natural occurrence of nanoparticles. AgNPs and AuNPs emanating from Ag(I)/Au(III)–NOM reactions are stable for several months, thus indicating their potential to be transported over long distances from their point of origin. However, endogenous cations present in natural waters can destabilize the nanoparticles, with divalent cations (e.g., Ca²⁺, Mg²⁺) being more influential than their monovalent equivalents (e.g., Na⁺, K⁺). The toxicity of NNPs may differ from that of ENPs because of differences in the coatings on the nanoparticle surfaces. An example of this phenomenon is presented and is briefly discussed.

Iron oxide nanoparticles have been intensively investigated owing to their huge potential as diagnostic, therapeutic, and drug-carrier agents in biomedicine, sorbents in environmental technologies, sensors of various inorganic and organic/biological substances, energy-generating and storing materials, and in assorted biotechnological and industrial processes involving microbiology, pigment industry, recording and magnetic media or (bio)catalysis. An eminent interest in exploring the realm of iron oxides is driven by their chemical and structural diversity, high abundance, low cost, non-toxicity, and broad portfolio of chemical procedures enabling their syntheses with desirable physicochemical features. The current review article centers its attention on the contemporary advancements in the field of catalysis and environmental technologies employing iron oxides in various chemical forms (e.g., hematite, magnetite, maghemite), sizes (∼10–100 nm), morphology characteristics (e.g., globular, needle-like), and nano architecture (e.g., nanoparticles, nanocomposites, core–shell structures). In particular, the catalytic applications of iron oxides and their hybrids are emphasized regarding their efficiency and selectivity in the coupling, oxidation, reduction, alkylation reactions, and Fischer–Tropsch synthesis. The deployment of iron oxides and their nanocomposites in environmental and water treatment technologies is also deliberated with their roles as nanosorbents for heavy metals and organic pollutants, photocatalysts, and heterogeneous catalysts (e.g., hydrogen peroxide decomposition) for oxidative treatment of various contaminants. The associated challenges and potential progress in iron-oxide-based catalytic and environmental technologies are highlighted as well. Young chemists, researchers, and scientists could find this review useful in enhancing the usefulness of nano iron oxides in their investigations and developing sustainable methodologies.