Previous studies have documented the antibacterial activity of certain iron-containing clays. However, the repulsion between negatively charged bacteria and the clay surface makes this process inefficient. The objective of this study is to improve the bactericidal efficiency of clays by reversing their surface charge from negative to positive. To achieve this objective, positively charged chitosan, a nontoxic and biodegradable polymer, was intercalated into nontronite NAu-2. Chitosan-intercalated NAu-2 (C-NAu-2) was chemically reduced to obtain reduced C-NAu-2 (rC-NAu-2). Relative to reduced nontronite (rNAu-2), the antibacterial activity of rC-NAu-2 is higher and more persistent over a pH range of 6–8. The close spatial association between positively charged rC-NAu-2 and negatively charged bacteria increases the chances of cell membrane attack by extracellular ROS, the influx of soluble Fe2+ into the bacterial cell, and the yield of intracellular ROS. All these factors contribute to the enhanced antibacterial activity of rC-NAu-2. In contrast to rNAu-2 treated E. coli cells, where membrane damage and intracellular ROS/Fe accumulation are restricted to the polar regions, the close bacteria–clay association in rC-NAu-2 results in nonselective membrane damage and more uniform intracellular ROS/Fe distribution across whole bacterial cells. These results advance the antibacterial model by highlighting the importance of bacteria–clay interactions to the antibacterial activity of Fe-bearing clays.

The mineral-microbe interactions play important roles in environmental change, biogeochemical cycling of elements, and formation of ore deposits. Minerals provide both beneficial (physical and chemical protection, nutrients, and energy) and detrimental (toxic substances and oxidative pressure) effects to microbes, resulting in mineral-specific microbial colonization. Microbes impact dissolution, transformation, and precipitation of minerals through their activity, resulting in either genetically-controlled or metabolism-induced biomineralization. Through these interactions minerals and microbes coevolve through Earth history. The mineral-microbe interactions typically occur at microscopic scale but the effect is often manifested at global scale. Despite advances achieved through decades of research, major questions remain. Four areas are identified for future research: integrating mineral and microbial ecology, establishing mineral biosignatures, linking laboratory mechanistic investigation to field observation, and manipulating mineral-microbe interactions for the benefit of humankind.

Reduced nontronite has been demonstrated to be antibacterial through the production of hydroxyl radical (•OH) from the oxidation of structural Fe­(II). Herein, we investigated the antibacterial activity of more common smectite–illite (S–I) clays toward Escherichia coli cells, including montmorillonite SWy-3, illite IMt-2, 50–50 S–I rectorite RAr-1, 30–70 S–I ISCz-1, and nontronite NAu-2. Under an oxic condition, reduced clays (with a prefix r before mineral names) produced reactive oxygen species (ROS), and the antibacterial activity followed the order of rRAr-1 > rSWy-3 ≥ rNAu-2 ≫ rIMt-2 ≥ rISCz-1. The strongest antibacterial activity of rRAr-1 was contributed by a combination of •OH and Fe­(IV) generated from structural Fe­(II)/adsorbed Fe2+ and soluble Fe2+, respectively. Higher levels of lipid and protein oxidation, intracellular ROS accumulation, and membrane disruption were consistent with this antibacterial mechanism of rRAr-1. The antibacterial activity of other S–I clays depended on layer expandability, which determined the reactivity of structural Fe­(II) and the production of •OH, with the expandable smectite being the most antibacterial and nonexpandable illite the least. Our results provide new insights into the antibacterial mechanisms of clay minerals.

Bioreduction of soluble U(VI) to sparingly soluble U(IV) solids was proposed as a remediation method for uranium contamination. Therefore, the stability and longevity of biogenic U(IV) are critical to the success of uranium remediation. However, co-occurrence of clay minerals and organic ligands could potentially reoxidize U(IV) to U(VI). Herein, we report a combined effect of Fe(III)-rich nontronite (NAu-2) and environmentally prevalent organic ligands on reoxidation of biogenic U(IV) at circumneutral pH. After 30 days of incubation, structural Fe(III) in NAu-2 oxidized 45.50% U(IV) with an initial rate of 2.7 × 10 −3 mol m −2 d −1 . Addition of citrate and ethylenediaminetetraacetic acid (EDTA) greatly promoted the oxidative dissolution of U(IV) by structural Fe(III) in NAu-2, primarily through the formation of aqueous ligand-U(IV) complexes. In contrast, a model siderophore, desferrioxamine B (DFOB), partially inhibited U(IV) oxidation due to the formation of stable DFOB-Fe 3+ complexes. The resulting U(VI) species intercalated into an NAu-2 interlayer or adsorbed onto an NAu-2 surface. Our results highlight the importance of organic ligands in oxidative dissolution of U(IV) minerals by Fe(III)-bearing clay minerals and have important implications for the design of nuclear waste storage and remediation strategies, especially in clay-and organic-rich environments.

Nylon membranes modified by gold nanoparticles as substrates showed preferable test reproducibility and appropriate sensitivity. This process provided a low-cost and reliable SERS testing strategy for qualitative and quantitative analysis.