An algorithm for the automatic deglitching of X-ray absorption spectroscopy data.

Analysis of X-ray absorption spectroscopy data often involves the removal of artifacts or glitches from the acquired signal, a process commonly known as deglitching. Glitches result either from specific orientations of monochromator crystals or from scattering by crystallites in the sample itself. Since the precise energy - or wavelength - location and the intensity of glitches in a spectrum cannot always be predicted, deglitching is often performed on a per spectrum basis by the analyst. Some routines have been proposed, but they are prone to arbitrary selection of spectral artifacts and are often inadequate for processing large data sets. Here, a statistically robust algorithm, implemented as a Python program, for the automatic detection and removal of glitches that can be applied to a large number of spectra, is presented. It uses a Savitzky-Golay filter to smooth spectra and the generalized extreme Studentized deviate test to identify outliers. Robust, repeatable, and selective removal of glitches is achieved using this algorithm.

Synergistic Bacterial Stress Results from Exposure to Nano-Ag and Nano-TiO2 Mixtures under Light in Environmental Media.

Due to their widespread use and subsequent release, engineered nanomaterials (ENMs) will create complex mixtures and emergent systems in the natural environment where their chemical interactions may cause toxic stress to microorganisms. We previously showed that under dark conditions n-TiO2 attenuated bacterial stress caused by low concentrations of n-Ag (<20 µg L-1) due to Ag+ adsorption, yet, since both n-Ag and n-TiO2 are photoactive, their photochemistries may play a key role in their interactions. In this work, we study the chemical interactions of n-Ag and n-TiO2 mixtures in a natural aqueous medium under simulated solar irradiation to investigate photoinduced stress. Using ATP levels and cell membrane integrity as probes, we observe that n-Ag and n-TiO2 together exert synergistic toxic stress in Escherichia coli. We find increased production of hydrogen peroxide by the n-Ag/n-TiO2 mixture, revealing that the enhanced photocatalytic activity and production of ROS likely contribute to the stress response observed. Based on STEM-EDS evidence, we propose that a new composite Ag/TiO2 nanomaterial forms under these conditions and explains the synergistic effects of the ENM mixture. Overall, this work reveals that environmental transformations of ENM mixtures under irradiation can enhance biological stress beyond that of individual components.

Spectroscopic and Microscopic Evidence of Biomediated HgS Species Formation from Hg(II)-Cysteine Complexes: Implications for Hg(II) Bioavailability.

We investigated the chemistry of Hg(II) during exposure of exponentially growing bacteria ( Escherichia coli, Bacillus subtilis, and Geobacter sulfurreducens) to 50 nM, 500 nM, and 5 µM total Hg(II) with and without added cysteine. With X-ray absorption spectroscopy, we provide direct evidence of the formation of cell-associated HgS for all tested bacteria. The addition of cysteine (100-1000 µM) promotes HgS formation (>70% of total cell-associated Hg(II)) as a result of the biodegradation of added cysteine to sulfide. Cell-associated HgS species are also detected when cysteine is not added as a sulfide source. Two phases of HgS, cinnabar (α-HgS) and metacinnabar (ß-HgS), form depending on the total concentration of Hg(II) and sulfide in the exposure medium. However, α-HgS exclusively forms in assays that contain an excess of cysteine. Scanning transmission electron microscopy images reveal that nanoparticulate HgS(s) is primarily located at the cell surface/extracellular matrix of Gram-negative E. coli and G. sulfurreducens and in the cytoplasm/cell membrane of Gram-positive B. subtilis. Intracellular Hg(II) was detected even when the predominant cell-associated species was HgS. This study shows that HgS species can form from exogenous thiol-containing ligands and endogenous sulfide in Hg(II) biouptake assays under nondissimilatory sulfate reducing conditions, providing new considerations for the interpretation of Hg(II) biouptake results.

Structural characterization of metal complexes in aqueous solutions: a XAS study of stannous fluoride.

The identity and structure of tin(ii)-fluoride complexes formed in aqueous solutions is determined by combining X-ray absorption spectroscopy, thermodynamic modeling and quantum mechanical calculations. Spectroscopic measurements confirm the presence of 3 stannous fluoride complexes, SnF+, SnF02 and SnF3-, with mean Sn-F bond distances that increase linearly, from 1.98 to about 2.04 Å, as a function of the coordination number. Computational ab initio calculations indicate that the stannous fluoride complexes form localized σs-p bonds, with the stereochemically active lone pair of the Sn(ii) atom distorting the geometry of the complexes. In addition, the SnF3- complex exhibits loosely coordinated water, which is removed upon addition of glycerol to lower the solvent activity. Our results provide spectroscopic confirmation of the stannous fluoride complexes proposed in the literature, and explain why glycerol additions stabilize solutions of Sn(ii) against oxidation.

Cysteine Addition Promotes Sulfide Production and 4-Fold Hg(II)-S Coordination in Actively Metabolizing Escherichia coli.

The bacterial uptake of mercury(II), Hg(II), is believed to be energy-dependent and is enhanced by cysteine in diverse species of bacteria under aerobic and anaerobic conditions. To gain insight into this Hg(II) biouptake pathway, we have employed X-ray absorption spectroscopy (XAS) to investigate the relationship between exogenous cysteine, cellular metabolism, cellular localization, and Hg(II) coordination in aerobically respiring Escherichia coli (E. coli). We show that cells harvested in exponential growth phase consistently display mixtures of 2-fold and 4-fold Hg(II) coordination to sulfur (Hg-S2 and Hg-S4), with added cysteine enhancing Hg-S4 formation. In contrast, cells in stationary growth phase or cells treated with a protonophore causing a decrease in cellular ATP predominantly contain Hg-S2, regardless of cysteine addition. Our XAS results favor metacinnabar (ß-HgS) as the Hg-S4 species, which we show is associated with both the cell envelope and cytoplasm. Additionally, we observe that added cysteine abiotically oxidizes to cystine and exponentially growing E. coli degrade high cysteine concentrations (100-1000 µM) into sulfide. Thermodynamic calculations confirm that cysteine-induced sulfide biosynthesis can promote the formation of dissolved and particulate Hg(II)-sulfide species. This report reveals new complexities arising in Hg(II) bioassays with cysteine and emphasizes the need for considering changes in chemical speciation as well as growth stage.

One-Time Addition of Nano-TiO2 Triggers Short-Term Responses in Benthic Bacterial Communities in Artificial Streams.

Nano-TiO2 is an engineered nanomaterial whose production and use are increasing rapidly. Hence, aquatic habitats are at risk for nano-TiO2 contamination due to potential inputs from urban and suburban runoff and domestic wastewater. Nano-TiO2 has been shown to be toxic to a wide range of aquatic organisms, but little is known about the effects of nano-TiO2 on benthic microbial communities. This study used artificial stream mesocosms to assess the effects of a single addition of nano-TiO2 (P25 at a final concentration of 1 mg l(-1)) on the abundance, activity, and community composition of sediment-associated bacterial communities. The addition of nano-TiO2 resulted in a rapid (within 1 day) decrease in bacterial abundance in artificial stream sediments, but bacterial abundance returned to control levels within 3 weeks. Pyrosequencing of partial 16S rRNA genes did not indicate any significant changes in the relative abundance of any bacterial taxa with nano-TiO2 treatment, indicating that nano-TiO2 was toxic to a broad range of bacterial taxa and that recovery of the bacterial communities was not driven by changes in community composition. Addition of nano-TiO2 also resulted in short-term increases in respiration rates and denitrification enzyme activity, with both returning to control levels within 3 weeks. The results of this study demonstrate that single-pulse additions of nano-TiO2 to aquatic habitats have the potential to significantly affect the abundance and activity of benthic microbial communities and suggest that interactions of TiO2 nanoparticles with environmental matrices may limit the duration of their toxicity.

Lifetime and dissolution kinetics of zinc oxide nanoparticles in aqueous media.

We have assessed the persistence and lifetime of ZnO nanoparticles (ZnO-NPs) by performing dissolution experiments in three different aqueous media. These experiments were performed at ZnO-NP concentration levels close to the solubility of zincite (∼8 µM or 650 µg l(-1) of ZnO)-a concentration that is orders of magnitude higher than current estimated relevant environmental concentrations. The kinetics were followed by voltammetry, while maintaining the pH at about 7.5 using a CO2/N2 gas mixture to remove di-oxygen interference. Our results show that, under these conditions, ZnO-NPs readily dissolve with a lifetime expectancy that does not exceed 90 min. Water chemistry, especially the presence of dissolved organic matter (DOM), plays an important role in ZnO-NP dissolution. Dissolution rates significantly increase in the presence of strong chelating agents, EDTA and L-cysteine, while the addition of polymeric DOM, such as sodium alginate, has the opposite effect. Our results suggest that ZnO-NPs are unlikely to persist in natural aqueous media and that the toxicity should be primarily related to the released Zn(2+) ions rather than effects commonly associated to the presence of nanoparticles.

Hydrodynamic Forcing Mobilizes Cu in Low-Permeability Estuarine Sediments.

Overlying hydrodynamics play critical roles in controlling surface-porewater exchanges in permeable sediments, but these effects have rarely been characterized in low-permeability sediments. We conducted a series of laboratory experiments to evaluate the effects of varied hydrodynamic conditions on the efflux of metals from low-permeability estuarine sediments. Two Cu-contaminated sediments obtained from the Piscataqua River were subject to controlled levels of hydrodynamic shear in Gust mesocosms, including episodic sediment resuspension. Overlying water and porewater samples were collected over the course of experiments and analyzed for metal concentrations. The two sediments had similar permeability (∼10(-15) m(2)), but different particle size distributions. Hydrodynamic forcing enhanced the mobilization and efflux of Cu from the coarser-grained sediments, but not the finer-grained sediments. Sediment resuspension caused additional transitory perturbations in Cu concentrations in the water column. Particulate metal concentrations increased significantly during resuspension, but then rapidly decreased to preresuspension levels following cessation of sediment transport. Overall, these results show that the mobility and efflux of metals are likely to be influenced by overlying hydrodynamics even in low-permeability sediments, and these effects are mediated by sediment heterogeneity and resuspension.

Attenuation of Microbial Stress Due to Nano-Ag and Nano-TiO2 Interactions under Dark Conditions.

Engineered nanomaterials (ENMs) are incorporated into thousands of commercial products, and their release into environmental systems creates complex mixtures with unknown toxicological outcomes. To explore this scenario, we probe the chemical and toxicological interactions of nanosilver (n-Ag) and nanotitania (n-TiO2) in Lake Michigan water, a natural aqueous medium, under dark conditions. We find that the presence of n-Ag induces a stress response in Escherichia coli, as indicated by a decrease in ATP production observed at low concentrations (in the µg L-1 range), with levels that are environmentally relevant. However, when n-Ag and n-TiO2 are present together in a mixture, n-TiO2 attenuates the toxicity of n-Ag at and below 20 µg L-1 by adsorbing Ag+(aq). We observe, however, that toxic stress cannot be explained by dissolved silver concentrations alone and, therefore, must also depend on silver associated with the nanoscale fraction. Although the attenuating effect of n-TiO2 on n-Ag's toxicity is limited, this study emphasizes the importance of probing the toxicity of ENM mixtures under environmental conditions to assess how chemical interactions between nanoparticles change the toxicological effects of single ENMs in unexpected ways.

Conformational changes during permeation of Na+ through a modified cyclic peptide nanotube promote energy landscape roughness.

Using a metadynamics approach, we investigate the potential of mean force for Na+ permeation inside a cyclic peptide nanotube (CPN) with modified interior as a function of ion position, coordination number, and lumen chemistry. We show that functionalizing the lumen of a CPN with a methyl-benzoic acid group introduces non-periodic variations in the internal energy of the nanotube, which dictate the overall free energy roughness during the permeation of Na+. These non-periodic variations arise from the structural dynamics of the functional group, where changes in the dihedral angles induced by the proximity of the ion give rise to conformational changes that increase landscape roughness and thereby decrease transport rate. Our computational framework emphasizes the advantages of using the coordination number as a collective variable to investigate the available conformations during ion permeation through CPNs, and reveals new structure-function relations for chemically tunable CPNs, paving the way for rational design of nano-porous systems with tunable selectivity and flux.

Coupled effects of hydrodynamics and biogeochemistry on Zn mobility and speciation in highly contaminated sediments.

Porewater transport and diagenetic reactions strongly regulate the mobility of metals in sediments. We executed a series of laboratory experiments in Gust chamber mesocosms to study the effects of hydrodynamics and biogeochemical transformations on the mobility and speciation of Zn in contaminated sediments from Lake DePue, IL. X-ray absorption spectroscopy (XAS) indicated that the oxidation of surficial sediments promoted the formation of more mobile Zn species. Bulk chemical measurements of porewater, overlying water, and sediment also suggested that this process liberated aqueous metals to porewater and facilitated Zn efflux to the overlying water. In addition, sediment resuspension events increased the release of aqueous metals to both surficial porewater and the overlying water column. XAS analysis indicated that resuspension increased dissolution of Zn-sequestering mineral phases. These results show that both steady slow porewater transport and rapid episodic resuspension are important to the release of metal from fine-grained, low-permeability contaminated sediments. Thus, information on metals speciation and mobility under time-varying overlying flow conditions is essential to understanding the long-term behavior of metals in contaminated sediments.

Combined Toxicity of Nano-ZnO and Nano-TiO2: From Single- to Multinanomaterial Systems.

Previous studies on the toxicity of engineered nanomaterials (ENMs) have been primarily based on testing individual ENMs, so little is known about the interactions and combined toxicity of multiple ENMs. In this study the toxicity of chemically stable nano-TiO2 and soluble nano-ZnO was investigated individually and in combination, by monitoring bacterial cell membrane integrity and ATP levels in a natural aqueous medium (Lake Michigan water). Both nano-TiO2 and nano-ZnO damage bacterial cell membranes under simulated solar irradiation (SSI), but their phototoxicity is not additive. Nano-ZnO at 1 mg/L, for example, surprisingly eliminates the damaging effect of nano-TiO2 at 10 mg/L. This phenomenon does not correlate with reactive oxygen species production, but is explained by a reduced extent of bacteria/nano-TiO2 contact in the presence of both nano-ZnO and dissolved zinc. The presence of nano-ZnO also exerts a significant decrease in bacterial ATP levels both under SSI and in the dark, a stress effect not captured by measuring bacterial cell membrane integrity. This inhibitory effect of nano-ZnO, however, is reduced somewhat by nano-TiO2 due to the adsorption of Zn(2+). Therefore, our results reveal that nanoparticle interactions and surface complexation reactions alter the original toxicity of individual nanoparticles and that comprehensive assessments of potential ENM toxicity in the environment require careful integration of complex physicochemical interactions between ENMs and various biological responses.

The molecular structure of aqueous Hg(II)-EDTA as determined by X-ray absorption spectroscopy.

The widespread presence and persistence of ethylenediaminetetraacetic acid (EDTA) in aquatic environments can lead to the formation of metal-EDTA complexes that influence metal bioavailability and mobility. Recently, the Hg(II)-EDTA complex was observed to slightly promote the biouptake of Hg(II) to the bacterium Escherichia coli and to undergo a relatively quick ligand exchange reaction with thiols at the bacterial cell membrane. The reactivity of a metal complex depends on its molecular structure; however, the molecular structure of aqueous Hg(II)-EDTA has yet to be reported. Here, we use X-ray absorption spectroscopy to determine the molecular structure of aqueous Hg(II)-EDTA. Our results suggest that aqueous Hg(II)-EDTA displays distorted octahedral geometry with one water molecule in the coordination sphere.

Chemical interactions between Nano-ZnO and Nano-TiO2 in a natural aqueous medium.

The use of diverse engineered nanomaterials (ENMs) potentially leads to the release of multiple ENMs into the environment. However, previous efforts to understand the behavior and the risks associated with ENMs have focused on only one material at a time. In this study, the chemical interactions between two of the most highly used ENMs, nano-TiO2, and nano-ZnO, were examined in a natural water matrix. The fate of nano-ZnO in Lake Michigan water was investigated in the presence of nano-TiO2. Our experiments demonstrate that the combined effects of ZnO dissolution and Zn adsorption onto nano-TiO2 control the concentration of dissolved zinc. X-ray absorption spectroscopy was used to determine the speciation of Zn in the particulate fraction. The spectra show that Zn partitions between nano-ZnO and Zn2+ adsorbed on nano-TiO2. A simple kinetic model is presented to explain the experimental data. It integrates the processes of nano-ZnO dissolution with Zn adsorption onto nano-TiO2 and successfully predicts dissolved Zn concentration in solution. Overall, our results suggest that the fate and toxicity potential of soluble ENMs, such as nano-ZnO, are likely to be influenced by the presence of other stable ENMs, such as nano-TiO2.

Dissolution kinetics of copper oxide nanoparticles in presence of glyphosate.

Recently CuO nanoparticles (n-CuO) have been proposed as an alternative method to deliver a Cu-based pesticide for controlling fungal infestations. With the concomitant use of glyphosate as an herbicide, the interactions between n-CuO and this strong ligand need to be assessed. We investigated the dissolution kinetics of n-CuO and bulk-CuO (b-CuO) particles in the presence of a commercial glyphosate product and compared it to oxalate, a natural ligand present in soil water. We performed experiments at concentration levels representative of the conditions under which n-CuO and glyphosate would be used (∼0.9 mg/L n-CuO and 50 µM of glyphosate). As tenorite (CuO) dissolution kinetics are known to be surface controlled, we determined that at pH 6.5, T âˆ¼ 20 °C, using KNO3 as background electrolyte, the presence of glyphosate leads to a dissolution rate of 9.3 ± 0.7 ×10-3 h-1. In contrast, in absence of glyphosate, and under the same conditions, it is 2 orders of magnitude less: 8.9 ± 3.6 ×10-5 h-1. In a more complex multi-electrolyte aqueous solution the same effect is observed; glyphosate promotes the dissolution rates of n-CuO and b-CuO within the first 10 h of reaction by a factor of ∼2 to ∼15. In the simple KNO3 electrolyte, oxalate leads to dissolution rates of CuO about two times faster than glyphosate. However, the kinetic rates within the first 10 h of reaction are about the same for the two ligands when the reaction takes place in the multi-electrolyte solution as oxalate is mostly bound to Ca2+ and Mg2+.

Polyaniline-metal oxide coatings for biocidal applications: Mechanisms of activation and deactivation.

Metal oxide (MO) coatings (e.g. TiO2, ZnO, and CuO) have shown great promise to inactivate pathogenic bacteria, maintain self-cleaning surfaces, and prevent infectious diseases spread via surface contact. Under light illumination, the antibacterial performance of photoactive MO coatings is determined by reactive oxygen species (ROS) generation. However, several drawbacks, such as photo-corrosion and rapid electron-hole recombination, hinder the ROS production of MO coatings and diminish their antibacterial efficiency. In this study, we employed polyaniline (PANI), an inexpensive and easy-to-synthesize conductive polymer, to fabricate polyaniline-metal oxide composite (PMC) films. The antibacterial performance of PMC films was tested using E. coli as the model bacterium and Lake Michigan water (LMW) as the background medium and revealed enhanced antibacterial performance relative to MO coatings alone (approximately 75-90 % kill of E. coli by PMC coatings in comparison to 20-40 % kill by MO coatings), which is explained by an increase in the ROS yields of PMC. However, with repeated use, the antibacterial performance of the PMC coatings is diminished due to deprotonation of the PANI in the neutral/slightly basic aqueous environment of LMW. Overall, PANI can enhance the antibacterial performance of MO coatings, but efforts need to be directed to preserve or regenerate PMC stability under environmental conditions and applications.

An XAS study of Hg(II) sorption to Al-based drinking water treatment residuals.

Drinking water treatment residuals (DWTRs) are produced from the coagulation and flocculation processes in conventional drinking water treatment. The abundant metal oxide content of these materials resulting from the use of coagulants, like alum and ferric chloride, has driven strong research interest into the reuse of DWTRs as sorptive materials. Using a suite of aluminum-based DWTRs, we provide new insights into Hg(II) sorption mechanisms. Experiments performed at circum-neutral pH show that sorption capacities are related to the amount of organic carbon/matter present in DWTRs. We found that carbon rich samples can scavenge about 9000 mg/kg of Hg, in contrast to 2000 mg/kg for lime based DWTRs. X-ray absorption spectroscopy (XAS) at the Hg L3 edge further characterizes mercury coordination. X-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) results point to a partial association of mercury with sulfur at low mass loadings, transitioning to a full association with oxygen/carbon at higher concentrations of sorbed Hg(II) and in DWTRs with limited sulfur content. These results suggest that sorption of Hg(II) is primarily controlled by the carbon/organic matter fraction of DWTRs, but not by the coagulants.

Effects of material morphology on the phototoxicity of nano-TiO2 to bacteria.

Nanostructured titania (nano-TiO2) is produced in diverse shapes, but it remains largely unknown how tuning the morphology of nano-TiO2 may alter its toxicity. Herein, we show that material morphology plays a critical role in regulating the phototoxicity of nano-TiO2 to bacteria. Low-dimensional nano-TiO2, including nanotubes, nanorods, and nanosheets, were synthesized hydrothermally, and their effects on the bacterial viability of Escherichia coli and Aeromonas hydrophila were compared to spherical nanostructures (anatase nanospheres and P25). Results reveal that TiO2 nanotubes and nanosheets are less phototoxic than their rod- and sphere-shape counterparts under simulated solar irradiation. None of the tested nano-TiO2 shows toxicity in the dark. In contrast to their diminished phototoxicity, however, TiO2 nanotubes and nanosheets exhibit comparable or even higher photoactivity than other nanostructures. Observations by scanning transmission electron microscopy suggest that material morphology influences nano-TiO2 phototoxicity by governing how nano-TiO2 particles align at the bacterial cell surface. Overall, when comparing materials with different morphologies and dimensionality, nano-TiO2 phototoxicity is not a simple function of photocatalytic reactivity or ROS production. Instead, we propose that the evaluation of nano-TiO2 phototoxicity encompasses a three-pronged approach, involving the intrinsic photoactivity, aggregation of nano-TiO2, and the nano-TiO2/bacteria surface interactions.

The impacts of metal-based engineered nanomaterial mixtures on microbial systems: A review.

The last decade has witnessed tremendous growth in the commercial use of metal-based engineered nanomaterials (ENMs) for a wide range of products and processes. Consequently, direct and indirect release into environmental systems may no longer be considered negligible or insignificant. Yet, there is an active debate as to whether there are real risks to human or ecological health with environmental exposure to ENMs. Previous research has focused primarily on the acute effects of individual ENMs using pure cultures under controlled laboratory environments, which may not accurately reveal the ecological impacts of ENMs under real environmental conditions. The goal of this review is to assess our current understanding of ENM effects as we move from exposure of single to multiple ENMs or microbial species. For instance, are ENMs' impacts on microbial communities predicted by their intrinsic physical or chemical characteristics or their effects on single microbial populations; how do chronic ENM interactions compare to acute toxicity; does behavior under simplified laboratory conditions reflect that in environmental media; finally, is biological stress modified by interactions in ENM mixtures relative to that of individual ENM? This review summarizes key findings and our evolving understanding of the ecological effects of ENMs under complex environmental conditions on microbial systems, identifies the gaps in our current knowledge, and indicates the direction of future research.

Acute and Chronic Toxicity Testing of Drinking Water Treatment Residuals in Freshwater Systems.

The beneficial use of drinking water treatment residuals (DWTRs) faces barriers due primarily to uncertainties and concerns about their potential environmental impacts. We used total and water leachable toxic metal concentrations and 2 benthic organism-based bioassays to identify suitable DWTR substrates for introduction to freshwater systems. Using total metal contents and the consensus probable effect concentration concept, 3 DWTRs were selected and used in elutriate and toxicity studies. The concentrations of water leachable Ag, As, Cd, Cu, Cr, Ni, Pb, and Zn were below the US Environmental Protection Agency's ambient water quality criteria. Using the long-term 65-d life cycle Chironomus tentans test and 4 different endpoints (survival, adult emergence, egg case production, and number of eggs produced per female), no statistical differences were found between the DWTR treatments and the controls. Similarly, results obtained using the 10-d Hyalella azteca test showed no toxicity. However, although both survival and growth were recorded in all bioassays, the results of the 10-d C. tentans and the 28-d H. azteca tests were ambiguous. For C. tentans, 2 of the 3 DWTRs resulted in significantly lower survival rates compared to the controls. For H. azteca, no significant growth differences were observed between controls and DWTR treatments, but 2 of the 3 DWTRs resulted in significantly lower survival rates than the controls. Overall, these results suggest that certain DWTR substrates could be suitable for introduction to aquatic systems. Environ Toxicol Chem 2021;40:2005-2014. © 2021 SETAC.