Biogenic Cyanide Production Promotes Dissolution of Gold Nanoparticles in Soil.

Gold nanoparticles (Au NPs) are often used to study the physiochemical behavior and distribution of nanomaterials in natural systems because they are assumed to be inert under environmental conditions, even though Au can be oxidized and dissolved by a common environmental compound: cyanide. We used the cyanogenic soil bacterium, Chromobacterium violaceum, to demonstrate that quorum-sensing-regulated cyanide production could lead to a high rate of oxidative dissolution of Au NPs in soil. After 7 days of incubation in a pH 7.0 soil inoculated with C. violaceum, labile Au concentration increased from 0 to 15%. There was no observable dissolution when Au NPs were incubated in abiotic soil. In the same soil adjusted to pH 7.5, labile Au concentration increased up to 29% over the same time frame. Furthermore, we demonstrated that Au dissolution required quorum-sensing-regulated cyanide production in soil by inoculating the soil with different cell densities and using a quorum-sensing-deficient mutant of C. violaceum, CV026. Au NP dissolution experiments in liquid media coupled with mass spectrometry analysis confirmed that biogenic cyanide oxidized Au NPs to soluble Au(CN)2-. These results demonstrate under which conditions biologically enhanced metal dissolution can contribute to the overall geochemical transformation kinetics of nanoparticle in soils, even though the materials may be inert in abiotic environments.

Geochemical control on uranium(IV) mobility in a mining-impacted wetland.

Wetlands often act as sinks for uranium and other trace elements. Our previous work at a mining-impacted wetland in France showed that a labile noncrystalline U(IV) species consisting of U(IV) bound to Al-P-Fe-Si aggregates was predominant in the soil at locations exhibiting a U-containing clay-rich layer within the top 30 cm. Additionally, in the porewater, the association of U(IV) with Fe(II) and organic matter colloids significantly increased U(IV) mobility in the wetland. In the present study, within the same wetland, we further demonstrate that the speciation of U at a location not impacted by the clay-rich layer is a different noncrystalline U(IV) species, consisting of U(IV) bound to organic matter in soil. We also show that the clay-poor location includes an abundant sulfate supply and active microbial sulfate reduction that induce substantial pyrite (FeS2) precipitation. As a result, Fe(II) concentrations in the porewater are much lower than those at clay-impacted zones. U porewater concentrations (0.02-0.26 µM) are also considerably lower than those at the clay-impacted locations (0.21-3.4 µM) resulting in minimal U mobility. In both cases, soil-associated U represents more than 99% of U in the wetland. We conclude that the low U mobility reported at clay-poor locations is due to the limited association of Fe(II) with organic matter colloids in porewater and/or higher stability of the noncrystalline U(IV) species in soil at those locations.

Rapid Physicochemical Changes in Microplastic Induced by Biofilm Formation.

Risk assessment of microplastic (MP) pollution requires understanding biodegradation processes and related changes in polymer properties. In the environment, there are two-way interactions between the MP properties and biofilm communities: (i) microorganisms may prefer some surfaces, and (ii) MP surface properties change during the colonization and weathering. In a 2-week experiment, we studied these interactions using three model plastic beads (polyethylene [PE], polypropylene [PP], and polystyrene [PS]) exposed to ambient bacterioplankton assemblage from the Baltic Sea; the control beads were exposed to bacteria-free water. For each polymer, the physicochemical properties (compression, crystallinity, surface chemistry, hydrophobicity, and surface topography) were compared before and after exposure under controlled laboratory conditions. Furthermore, we characterized the bacterial communities on the MP surfaces using 16S rRNA gene sequencing and correlated community diversity to the physicochemical properties of the MP. Significant changes in PE crystallinity, PP stiffness, and PS maximum compression were observed as a result of exposure to bacteria. Moreover, there were significant correlations between bacterial diversity and some physicochemical characteristics (crystallinity, stiffness, and surface roughness). These changes coincided with variation in the relative abundance of unique OTUs, mostly related to the PE samples having significantly higher contribution of Sphingobium, Novosphingobium, and uncultured Planctomycetaceae compared to the other test materials, whereas PP and PS samples had significantly higher abundance of Sphingobacteriales and Alphaproteobacteria, indicating possible involvement of these taxa in the initial biodegradation steps. Our findings demonstrate measurable signs of MP weathering under short-term exposure to environmentally relevant microbial communities at conditions resembling those in the water column. A systematic approach for the characterization of the biodegrading capacity in different systems will improve the risk assessment of plastic litter in aquatic environments.

Quorum Sensing Signals Form Complexes with Ag+ and Cu2+ Cations.

Quorum sensing (QS) regulates important bacterial behaviors such as virulent protein production and biofilm formation. QS requires that molecular signals are exchanged between cells, extracellularly, where environmental conditions influence signal stability. In this work, we present a novel complexation between metal cations (Ag+ and Cu2+) and a QS autoinducer signal, N-hexanoyl- L-homoserine lactone (HHL). The molecular interactions were investigated using mass spectrometery, attenuated total reflectance-Fourier transform infrared spectroscopy, and computational simulations. Results show that HHL forms predominantly 1:1 complexes with Ag+ ( Kd = 3.41 × 10-4 M) or Cu2+ ( Kd = 1.40 × 10-5 M), with the coordination chemistry occurring on the oxygen moieties. In vivo experiments with Chromobacterium violaceum CV026 show that sublethal concentrations of Ag+ and Cu2+ decreased HHL-regulated QS activity. Furthermore, when Ag+ was preincubated with HHL, Ag+ toxicity to CV026 decreased by an order of magnitude, suggesting HHL:metal complexes alter the bioavailability of the individual constituents.

Gold nanoparticle biodissolution by a freshwater macrophyte and its associated microbiome.

Predicting nanoparticle fate in aquatic environments requires mimicking of ecosystem complexity to observe the geochemical processes affecting their behaviour. Here, 12 nm Au nanoparticles were added weekly to large-scale freshwater wetland mesocosms. After six months, ~70% of Au was associated with the macrophyte Egeria densa, where, despite the thermodynamic stability of Au0 in water, the pristine Au0 nanoparticles were fully oxidized and complexed to cyanide, hydroxyls or thiol ligands. Extracted biofilms growing on E. densa leaves were shown to dissolve Au nanoparticles within days. The Au biodissolution rate was highest for the biofilm with the lowest prevalence of metal-resistant taxa but the highest ability to release cyanide, known to promote Au0 oxidation and complexation. Macrophytes and the associated microbiome thus form a biologically active system that can be a major sink for nanoparticle accumulation and transformations. Nanoparticle biotransformation in these compartments should not be ignored, even for nanoparticles commonly considered to be stable in the environment.

Disruption of Autolysis in Bacillus subtilis using TiO2 Nanoparticles.

In contrast to many nanotoxicity studies where nanoparticles (NPs) are observed to be toxic or reduce viable cells in a population of bacteria, we observed that increasing concentration of TiO2 NPs increased the cell survival of Bacillus subtilis in autolysis-inducing buffer by 0.5 to 5 orders of magnitude over an 8 hour exposure. Molecular investigations revealed that TiO2 NPs prevent or delay cell autolysis, an important survival and growth-regulating process in bacterial populations. Overall, the results suggest two potential mechanisms for the disruption of autolysis by TiO2 NPs in a concentration dependent manner: (i) directly, through TiO2 NP deposition on the cell wall, delaying the collapse of the protonmotive-force and preventing the onset of autolysis; and (ii) indirectly, through adsorption of autolysins on TiO2 NP, limiting the activity of released autolysins and preventing further lytic activity. Enhanced darkfield microscopy coupled to hyperspectral analysis was used to map TiO2 deposition on B. subtilis cell walls and released enzymes, supporting both mechanisms of autolysis interference. The disruption of autolysis in B. subtilis cultures by TiO2 NPs suggests the mechanisms and kinetics of cell death may be influenced by nano-scale metal oxide materials, which are abundant in natural systems.

Effects of UV-C and Vacuum-UV TiO2 Advanced Oxidation Processes on the Acute Mortality of Microalgae.

Advanced oxidation processes/technologies (AOT) that combine a semiconductor, such as titanium dioxide (TiO2 ), with a UV source have been used to eliminate microorganisms in various water treatment applications. To facilitate the applicability of this technique, the gain in efficiency from the semiconductor compared to the UV source alone with respect to different target organisms requires evaluation. The primary objective of this study was to determine the effects of TiO2 and UV wavelength on a freshwater alga, Pseudokirchneriella subcapitata and a marine alga, Tetraselmis suecica. For each species, dose-response experiments were conducted to determine the median lethal dose (LC50 ) of the following treatments: UV light emitted with a peak of 254 nm, UV light emitted with a peak of 254 nm in the presence of TiO2 and UV light emitted with a peak of 254 and 185 nm in the presence of TiO2 . In both species, the presence of TiO2 significantly increased mortality. Across all three treatments, P. subcapitata was more sensitive than T. suecica; moreover, the addition of the 185 nm wavelength significantly increased cell mortality in P. subcapitata but not in T. suecica.