Toxicity Of Ag Research Articles

Room Temperature Cation Exchange Reaction in Nanocrystals for Ultrasensitive Speciation Analysis of Silver Ions and Silver Nanoparticles.

To evaluate the toxicity of silver nanoparticles (AgNPs) and Ag(+) and gain deep insight into the transformation of AgNPs in the environment or organisms, ultrasensitive analytical methods are needed for their speciation analysis. About 40-fold of Cd(2+) in CdTe ionic nanocrystals can be "bombarded-and-exploded" (exchanged) in less than 1 min simply by mixing the nanocrystals with Ag(+) solution at room temperature, while this cation exchange reaction did not occur when only silver nanoparticles were present. On the basis of this striking difference, an ultrasensitive method was developed for speciation analysis of Ag(+) and AgNPs in complex matrices. The released Cd(2+) was reduced to its volatile species by sodium tetrahydroborate, which was separated and swept to an inductively coupled plasma mass spectrometer (ICPMS) or an atomic fluorescence spectrometer (AFS) for the indirect but ultrasensitive detection of Ag(+). Owing to the remarkable signal amplification via the cation exchange reaction and the advantages of chemical vapor generation for sampling, the limit of detection was 0.0003 μg L(-1) for Ag(+) by ICPMS, which was improved by 100-fold compared to the conventional method. Relative standard deviations are better than 2.5% at a concentration of 0.5 μg L(-1) Ag(+) or AgNPs regardless of the detector. The proposed method retains several unique advantages, including ultrahigh sensitivity, speciation analysis, simplicity and being organic reagent-free, and has been successfully utilized for speciation analysis of Ag(+) and AgNPs in environmental water samples and paramecium cells.

Phytotoxicity, uptake, and accumulation of silver with different particle sizes and chemical forms

The antimicrobial property of silver nanoparticles (AgNPs) makes it one of the most commonly encountered nanomaterials in commercial products. Consequently, its detection in the environment is highly likely and its potential toxicity has been heavily investigated. While it is now generally agreed that AgNP itself exerts unique toxicity to plants in addition to that of dissolved silver ion, the accumulation and fate of different forms of silver in plant tissues are unknown. This study investigates the phytotoxicity, accumulation, and transport of Ag with different physical and chemical characteristics (e.g., ionic, nanoparticles, and bulk) in two agricultural crop species: Glycine max (soybean) and Triticum aestivum (wheat). The results showed that different forms of Ag demonstrated differential toxicity in these two species, with the Ag+ at the same nominal concentration displaying the strongest effect on plant growth. Exposure to 5 mg/L of elemental Ag in different forms all resulted in significant deposition on the root surface but its morphology and distribution patterns varied considerably. The Ag transport efficiency from roots to shoots differed with both Ag type and plant species. Notably, the upward transport of AgNPs (20–50 nm) was considerably more substantial than that of bulk Ag (1–3 µm). Cell fractionation studies confirmed that all types of Ag were internalized, with the plant cell wall as the predominant place for element accumulation. The findings demonstrate that Ag toxicity and in planta fate vary with particle type and that such considerations are likely necessary to adequately assess food safety concerns upon NP exposure.

Sunlight-driven reduction of silver ion to silver nanoparticle by organic matter mitigates the acute toxicity of silver to Daphnia magna

Due to the unique antibacterial activities, silver nanoparticles (AgNPs) have been extensively used in commercial products. Anthropogenic activities have released considerable AgNPs as well as highly toxic silver ion (Ag+) into the aquatic environment. Our recent study revealed that ubiquitous natural organic matter (NOM) could reduce Ag+ to AgNP under natural sunlight. However, the toxic effect of this process is not well understood. In this work, we prepared mixture solution of Ag+ and AgNPs with varied Ag+% through the sunlight-driven reduction of Ag+ by NOM and investigated the acute toxicity of the solutions on Daphnia magna. Formation of AgNPs was demonstrated and characterized by comprehensive techniques and the fraction of unconverted Ag+ was determined by ultrafiltration-inductively coupled plasma mass spectrometry determination. The formation of AgNPs enhanced significantly with the increasing of solution pH and cumulative photosynthetically active radiation of sunlight. The toxicity of the resulting solution was further investigated by using freshwater crustacean D. magna as a model and an 8hr-median lethal concentration (LC50) demonstrated that the reduction of Ag+ by NOM to AgNPs significantly mitigated the acute toxicity of silver. These results highlight the importance of sunlight and NOM in the fate, transformation and toxicity of Ag+ and AgNPs, and further indicate that the acute toxicity of AgNPs should be mainly ascribed to the dissolved Ag+ from AgNPs.

Humic substances alleviate the aquatic toxicity of polyvinylpyrrolidone-coated silver nanoparticles to organisms of different trophic levels.

The present study investigated how humic substances (HS) modify the aquatic toxicity of silver nanoparticles (AgNPs) as these particles agglomerate in water and interact with HS. An alga species (Raphidocelis subcapitata), a cladoceran species (Chydorus sphaericus), and a freshwater fish larva (Danio rerio), representing organisms of different trophic levels, were exposed to colloids of the polyvinylpyrrolidone-coated AgNPs in the presence and absence of HS. Results show that the presence of HS alleviated the aquatic toxicity of the AgNP colloids to all the organisms in a dose-dependent manner. The particle size distribution of the AgNPs' colloidal particles shifted to lower values due to the presence of HS, implying that the decrease in the toxicity of the AgNP colloids cannot be explained by the variation of agglomeration size. The surface charge of the AgNPs was found to be more negative in the presence of high concentrations of HS, suggesting an electrostatic barrier by which HS might limit interactions between particles and algae cells; indeed, this effect reduced the algae toxicity. Observations on silver ions (Ag(+)) release show that HS inhibit AgNP dissolution, depending on the concentrations of HS. When toxic effects were expressed as a function of each Ag-species, toxicity of the free Ag(+) was found to be much higher than that of the agglomerated particles.

Speciation and lability of Ag-, AgCl-, and Ag2S-nanoparticles in soil determined by X-ray absorption spectroscopy and diffusive gradients in thin films.

Long-term speciation and lability of silver (Ag-), silver chloride (AgCl-), and silver sulfide nanoparticles (Ag2S-NPs) in soil were studied by X-ray absorption spectroscopy (XAS), and newly developed “nano” Diffusive Gradients in Thin Films (DGT) devices. These nano-DGT devices were designed specifically to avoid confounding effects when measuring element lability in the presence of nanoparticles. The aging profile and stabilities of the three nanoparticles and AgNO3 (ionic Ag) in soil were examined at three different soil pH values over a period of up to 7 months. Transformation of ionic Ag, Ag-NP and AgCl-NPs were dependent on pH. AgCl formation and persistence was observed under acidic conditions, whereas sulfur-bound forms of Ag dominated in neutral to alkaline soils. Ag2S-NPs were found to be very stable under all conditions tested and remained sulfur bound after 7 months of incubation. Ag lability was characteristically low in soils containing Ag2S-NPs. Other forms of Ag were linked to higher DGT-determined lability, and this varied as a function of aging and related speciation changes as determined by XAS. These results clearly indicate that Ag2S-NPs, which are the most environmentally relevant form of Ag that enter soils, are chemically stable and have profoundly low Ag lability over extended periods. This may minimize the long-term risks of Ag toxicity in the soil environment.

Toxicokinetic Toxicodynamic (TKTD) Modeling of Ag Toxicity in Freshwater Organisms: Whole-Body Sodium Loss Predicts Acute Mortality Across Aquatic Species

ToxicoKinetic ToxicoDynamic (TKTD) models are considered essential tools to further advance acute toxicity prediction of metals for a range of species and exposure conditions, but they are currently underutilized. We present a mechanistic TKTD model for acute toxicity prediction of silver (Ag) in freshwater organisms. In this new approach, we explicitly link relevant TKTD processes to species (physiological) characteristics, which facilitates model application to other untested freshwater organisms. The model quantifies the reduction in whole-body sodium concentration over time as a function of the target site inhibition over time, the target site density and the species-specific sodium turnover rate. Freshwater species are assumed to die instantly when they have lost a critical amount of their initial whole-body sodium concentration. Results show that mortality is significantly related to sodium loss (r(2) = 0.86) for various aquatic organisms and exposure durations. The model accurately predicts lethal effect concentrations for different freshwater organisms, including Daphnia magna, rainbow trout and juvenile crayfish, and is able to capture the observed size-specific variation of nearly 2 orders of magnitude in empirical LC50s.

Effect of toxicity of Ag nanoparticles on SERS spectral variance of bacteria

Ag nanoparticles (NPs) have been extensively utilized in surface-enhanced Raman scattering (SERS) spectroscopy for bacterial identification. However, Ag NPs are toxic to bacteria. Whether such toxicity can affect SERS features of bacteria and interfere with bacterial identification is still unknown and needed to explore. Here, by carrying out a comparative study on non-toxic Au NPs with that on toxic Ag NPs, we investigated the influence of nanoparticle concentration and incubation time on bacterial SERS spectral variance, both of which were demonstrated to be closely related to the toxicity of Ag NPs. Sensitive spectral alterations were observed on Ag NPs with increase of NPs concentration or incubation time, accompanied with an obvious decrease in number of viable bacteria. In contrast, SERS spectra and viable bacterial number on Au NPs were rather constant under the same conditions. A further analysis on spectral changes demonstrated that it was cell response (i.e. metabolic activity or death) to the toxicity of Ag NPs causing spectral variance. However, biochemical responses to the toxicity of Ag were very different in different bacteria, indicating the complex toxic mechanism of Ag NPs. Ag NPs are toxic to a great variety of organisms, including bacteria, fungi, algae, protozoa etc., therefore, this work will be helpful in guiding the future application of SERS technique in various complex biological systems.

Delineating ion-ion interactions by electrostatic modeling for predicting rhizotoxicity of metal mixtures to lettuce Lactuca sativa.

Effects of ion-ion interactions on metal toxicity to lettuce Lactuca sativa were studied based on the electrical potential at the plasma membrane surface (ψ0 ). Surface interactions at the proximate outside of the membrane influenced ion activities at the plasma membrane surface ({M(n+)}0). At a given free Cu(2+) activity in the bulk medium ({Cu(2+)}b), additions of Na(+), K(+), Ca(2+), and Mg(2+) resulted in substantial decreases in {Cu(2+)}0. Additions of Zn(2+) led to declines in {Cu(2+)}0, but Cu(2+) and Ag(+) at the exposure levels tested had negligible effects on the plasma membrane surface activity of each other. Metal toxicity was expressed by the {M(n+)}0 -based strength coefficient, indicating a decrease of toxicity in the order: Ag(+) > Cu(2+) > Zn(2+). Adsorbed Na(+), K(+), Ca(2+), and Mg(2+) had significant and dose-dependent effects on Cu(2+) toxicity in terms of osmolarity. Internal interactions between Cu(2+) and Zn(2+) and between Cu(2+) and Ag(+) were modeled by expanding the strength coefficients in concentration addition and response multiplication models. These extended models consistently indicated that Zn(2+) significantly alleviated Cu(2+) toxicity. According to the extended concentration addition model, Ag(+) significantly enhanced Cu(2+) toxicity whereas Cu(2+) reduced Ag(+) toxicity. By contrast, the response multiplication model predicted insignificant effects of adsorbed Cu(2+) and Ag(+) on the toxicity of each other. These interactions were interpreted using ψ0, demonstrating its influence on metal toxicity.

Influence of Water Hardness on Silver Ion and Silver Nanoparticle Fate and Toxicity Toward Nitrosomonas europaea.

This study investigated the influence of water hardness (Mg2+ and Ca2+) on the fate and toxicity of 20 nm citrate silver nanoparticles (AgNPs) and Ag+ toward Nitrosomonas europaea, a model ammonia-oxidizing bacterium. Nitrification inhibition of N. europaea by 1 ppm AgNPs and 0.5 ppm Ag+ was reduced from 80% and 83%, respectively, in the absence of Mg2+ to 2% and 33%, respectively, in the presence of 730 μM Mg2+. Introduction of Mg2+ resulted in the rapid aggregation of the AgNP suspensions and reduced the 3 h Ag+ dissolution rates from 30%, in the absence of Mg2+, to 9%, in the presence of 730 μM Mg2+. Reduced AgNP dissolution rates resulted in decreased concentrations of silver that were found adsorbed to N. europaea cells. Increasing AgNP concentrations in the presence of Mg2+ increased the observed inhibition of nitrification, but was always less than what was observed in the absence of Mg2+. The presence of Mg2+ also reduced the adsorption of Ag+ to cells, possibly due to multiple mechanisms, including a reduction in the negative surface charge of the N. europaea membrane and a competition between Mg2+ and Ag+ for membrane binding sites and transport into the cells. Ca2+ demonstrated similar protection mechanisms, as Ag+ toxicity was reduced and AgNP suspensions aggregated and decreased their dissolution rates. These results indicate that the toxicity of Ag+ and AgNPs to nitrifying bacteria in wastewater treatment would be less pronounced in systems with hard water.

Heavy Metal Uptake and Toxicity in the Presence of Titanium Dioxide Nanoparticles: A Factorial Approach Using Daphnia magna.

Unintentionally released titanium dioxide nanoparticles (nTiO2) may co-occur in aquatic environments together with other stressors, such as, metal ions. The effects of P25-nTiO2 on the toxicity and uptake of the elements silver (Ag), arsenic (As) and copper (Cu) were assessed by applying a factorial test design. The test design consisted of two developmental stages of Daphnia magna, two levels of nTiO2 (0 versus 2 mg/L) as well as seven nominal test concentrations of the respective element. The presence of nTiO2 increased Ag toxicity for juveniles as indicated by a 40% lower 72-h EC50, while the toxicities of As and Cu were reduced by up to 80%. This reduction was even more pronounced for Cu in the presence of dissolved organic carbon (i.e., seaweed extract) and nTiO2. This outcome coincides with the body burden of the elements, which was elevated 2-fold for Ag and decreased 14-fold for Cu in the presence of nTiO2. Although the underlying mechanisms could not be uncovered, the data suggest that the carrier function of nTiO2 plays a central role. However, to understand the processes and mechanisms occurring in the field due to the presence of nTiO2 further systematic investigations considering environmental variables and nanoparticle characteristics are required.

Coexistence of silver and titanium dioxide nanoparticles: Enhancing or reducing environmental risks?

Due to their bactericidal and photocatalytic characteristics, silver nanoparticles (Ag NPs) and titanium dioxide nanoparticles (TiO2 NPs) are widely used in the fields of environment and physiology. Once these untreated nanoparticles are released into an aquatic environment and encounter one another, there is more uncertainty about their fate and ecotoxicological risks compared with the single nanoparticles. To expand our knowledge of the health and environmental impacts of nanoparticles, we investigated the possible risk of the co-existence of TiO2 NPs and Ag NPs in an aquatic environment using ciliated protozoa (Tetrahymena pyriformis) as an aquatic animal model. In this study, silver ion (Ag+) release and physicochemical properties, as well as their effect on oxidative stress biomarkers, were monitored. Continuous illumination (12,000lx) led to the 20.0% decrease in Ag+ release in comparison with dark conditions, while TiO2 NPs and continuous illumination resulted in decreasing the Ag+ concentration to 64.3% in contrast with Ag NPs-only suspensions. Toxicity tests indicated that different illumination modes exerted distinct effects of TiO2 NPs on the toxicity of Ag NPs: no effects, antagonism and synergism in dark, natural light and continuous light, respectively. In the presence of 1.5mg/L (18.8μM) TiO2 NPs, the toxicity of 1.5mg/L (13.9μM) Ag NPs was reduced by 28.7% and increased by 6.93% in natural light and 12,000lx of continuous light, respectively. After culturing in 12,000lx continuous light for 24h, SOD activity of the light control surged to 1.96 times compared to the dark control (P<0.001). TiO2 NPs induced a reduction of CAT activity by an average of (36.1±1.7) % in the light. In the natural light reductions in the toxicity of Ag, NPs decrease Ag+ concentrations via adsorption of Ag+ onto TiO2 NPs surfaces. The enhancement of Ag NPs toxicity can contribute to the formation of activated TiO2–Ag NPs complexes in continuous light. The existence of TiO2 NPs in various illumination modes changed the surface chemistry of Ag NPs and then led to different toxicity effects. TiO2 NPs reduce the environmental risks of Ag NPs in natural light, but in continuous light, TiO2 NPs enhance the environmental risks of Ag NPs.

The Effect of Size on Ag Nanosphere Toxicity in Macrophage Cell Models and Lung Epithelial Cell Lines Is Dependent on Particle Dissolution

Silver (Ag) nanomaterials are increasingly used in a variety of commercial applications. This study examined the effect of size (20 and 110 nm) and surface stabilization (citrate and PVP coatings) on toxicity, particle uptake and NLRP3 inflammasome activation in a variety of macrophage and epithelial cell lines. The results indicated that smaller Ag (20 nm), regardless of coating, were more toxic in both cell types and most active in the THP-1 macrophages. TEM imaging demonstrated that 20 nm Ag nanospheres dissolved more rapidly than 110 nm Ag nanospheres in acidic phagolysosomes consistent with Ag ion mediated toxicity. In addition, there were some significant differences in epithelial cell line in vitro exposure models. The order of the epithelial cell lines’ sensitivity to Ag was LA4 > MLE12 > C10. The macrophage sensitivity to Ag toxicity was C57BL/6 AM > MARCO null AM, which indicated that the MARCO receptor was involved in uptake of the negatively charged Ag particles. These results support the idea that Ag nanosphere toxicity and NLRP3 inflammasome activation are determined by the rate of surface dissolution, which is based on relative surface area. This study highlights the importance of utilizing multiple models for in vitro studies to evaluate nanomaterials.

Silver Nanoparticles and Growth Factors Incorporated Hydroxyapatite Coatings on Metallic Implant Surfaces for Enhancement of Osteoinductivity and Antibacterial Properties

Research on incorporation of both growth factors and silver (Ag) into hydroxyapatite (HA) coatings on metallic implant surfaces for enhancing osteoinductivity and antibacterial properties is a challenging work. Generally, Ag nanoparticles are easy to agglomerate and lead to a large increase in local Ag concentration, which could potentially affect cell activity. On the other hand, growth factors immobilization requires mild processing conditions so as to maintain their activities. In this study, bone morphology protein-2 (BMP-2) and Ag nanoparticle contained HA coatings were prepared on Ti surfaces by combining electrochemical deposition (ED) of Ag and electrostatic immobilization of BMP-2. During the ED process, chitosan (CS) was selected as the stabilizing agent to chelate Ag ions and generate Ag nanoparticles that are uniformly distributed in the coatings. CS also reduces Ag toxicity while retaining its antibacterial activity. Afterwards, a BMP/heparin solution was absorbed on the CS/Ag/HA coatings. Consequently, BMP-2 was immobilized on the coatings by the electrostatic attraction between CS, heparin, and BMP-2. Sustained release of BMP-2 and Ag ions from HA coatings was successfully demonstrated for a long period. Results of antibacterial tests indicate that the CS/Ag/HA coatings have high antibacterial properties against both Staphylococcus epidermidis and Escherichia coli. Osteoblasts (OB) culture reveals that the CS/Ag/HA coatings exhibit good biocompatibility. Bone marrow stromal cells (BMSCs) culture indicates that the BMP/CS/Ag/HA coatings have good osteoinductivity and promote the differentiation of BMSCs. Ti bars with BMP/CS/Ag/HA coatings were implanted into the femur of rabbits to evaluate the osteoinductivity of the coatings. Results indicate that BMP/CS/Ag/HA coatings favor bone formation in vivo. In summary, this study presents a convenient and effective method for the incorporation of growth factors and antibacterial agents into HA coatings. This method can be utilized to modify a variety of metallic implant surfaces.

Inactivation of the antibacterial and cytotoxic properties of silver ions by biologically relevant compounds.

There has been a recent surge in the use of silver as an antimicrobial agent in a wide range of domestic and clinical products, intended to prevent or treat bacterial infections and reduce bacterial colonization of surfaces. It has been reported that the antibacterial and cytotoxic properties of silver are affected by the assay conditions, particularly the type of growth media used in vitro. The toxicity of Ag+ to bacterial cells is comparable to that of human cells. We demonstrate that biologically relevant compounds such as glutathione, cysteine and human blood components significantly reduce the toxicity of silver ions to clinically relevant pathogenic bacteria and primary human dermal fibroblasts (skin cells). Bacteria are able to grow normally in the presence of silver nitrate at >20-fold the minimum inhibitory concentration (MIC) if Ag+ and thiols are added in a 1∶1 ratio because the reaction of Ag+ with extracellular thiols prevents silver ions from interacting with cells. Extracellular thiols and human serum also significantly reduce the antimicrobial activity of silver wound dressings Aquacel-Ag (Convatec) and Acticoat (Smith & Nephew) to Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli in vitro. These results have important implications for the deployment of silver as an antimicrobial agent in environments exposed to biological tissue or secretions. Significant amounts of money and effort have been directed at the development of silver-coated medical devices (e.g. dressings, catheters, implants). We believe our findings are essential for the effective design and testing of antimicrobial silver coatings.

The effect of soil properties on the toxicity of silver to the soil nitrification process

Silver (Ag) is being increasingly used in a range of consumer products, predominantly as an antimicrobial agent, leading to a higher likelihood of its release into the environment. The present study investigated the toxicity of Ag to the nitrification process in European and Australian soils in both leached and unleached conditions. Overall, leaching of soils was found to have a minimal effect on the final toxicity data, with an average leaching factor of approximately 1. Across the soils, the toxicity was found to vary by several orders of magnitude, with concentrations of Ag causing a 50% reduction in nitrification relative to the controls (EC50) ranging from 0.43 mg Ag/kg to >640 mg Ag/kg. Interestingly, the dose-response relationships in most of the soils showed significant stimulation in nitrification at low Ag concentrations (i.e., hormesis), which in some cases produced responses up to double that observed in the controls. Soil pH and organic carbon were the properties found to have the greatest influence on the variations in toxicity thresholds across the soils, and significant relationships were developed that accounted for approximately 90% of the variability in the data. The toxicity relationships developed from the present study will assist in future assessment of potential Ag risks and enable the site-specific prediction of Ag toxicity.

Does water chemistry affect the dietary uptake and toxicity of silver nanoparticles by the freshwater snail Lymnaea stagnalis?

Silver nanoparticles (AgNPs) are widely used in many applications and likely released into the aquatic environment. There is increasing evidence that Ag is efficiently delivered to aquatic organisms from AgNPs after aqueous and dietary exposures. Accumulation of AgNPs through the diet can damage digestion and adversely affect growth. It is well recognized that aspects of water quality, such as hardness, affect the bioavailability and toxicity of waterborne Ag. However, the influence of water chemistry on the bioavailability and toxicity of dietborne AgNPs to aquatic invertebrates is largely unknown. Here we characterize for the first time the effects of water hardness and humic acids on the bioaccumulation and toxicity of AgNPs coated with polyvinyl pyrrolidone (PVP) to the freshwater snail Lymnaea stagnalis after dietary exposures. Our results indicate that bioaccumulation and toxicity of Ag from PVP-AgNPs ingested with food are not affected by water hardness and by humic acids, although both could affect interactions with the biological membrane and trigger nanoparticle transformations. Snails efficiently assimilated Ag from the PVP-AgNPs mixed with diatoms (Ag assimilation efficiencies ranged from 82 to 93%). Rate constants of Ag uptake from food were similar across the entire range of water hardness and humic acid concentrations. These results suggest that correcting regulations for water quality could be irrelevant and ineffective where dietary exposure is important.

Morphology-dependent bactericidal activities of Ag/CeO2 catalysts against Escherichia coli

Silver-loaded CeO2 nanomaterials (Ag/CeO2) including Ag/CeO2 nanorods, nanocubes, nanoparticles were prepared with hydrothermal and impregnation methods. Catalytic inactivation of Escherichia coli with Ag/CeO2 catalysts through the formation of reactive oxygen species (ROS) was investigated. For comparison purposes, the bactericidal activities of CeO2 nanorods, nanocubes and nanoparticles were also studied. There was a 3–4 log order improvement in the inactivation of E. coli with Ag/CeO2 catalysts compared with CeO2 catalysts. Temperature-programmed reduction of H2 showed that Ag/CeO2 catalysts had higher catalytic oxidation ability than CeO2 catalysts, which was the reason for that Ag/CeO2 catalysts exhibited stronger bactericidal activities than CeO2 catalysts. Further, the bactericidal activities of CeO2 and Ag/CeO2 depend on their shapes. Results of 5,5-dimethyl-1-pyrroline-N-oxide spin-trapping measurements by electron spin resonance and addition of catalase as a scavenger indicated the formation of OH, O2−, and H2O2, which caused the obvious bactericidal activity of catalysts. The stronger chemical bond between Ag and CeO2 nanorods led to lower Ag+ elution concentrations. The toxicity of Ag+ eluted from the catalysts did not play an important role during the bactericidal process. Experimental results also indicated that Ag/CeO2 induced the production of intracellular ROS and disruption of the cell wall and cell membrane. A possible production mechanism of ROS and bactericidal mechanism of catalytic oxidation were proposed.

Excellent antimicrobial properties of silver-loaded mesoporous silica SBA-15.

AimsTo synthesize silver‐loaded mesoporous silica SBA‐15 (Ag/SBA‐15) materials and examine their antimicrobial action and antimicrobial mechanism.Methods and ResultsAg/SBA‐15 materials were prepared by means of incipient wetness impregnation, impregnation and direct hydrothermal synthesis methods. The antimicrobial activity of Ag/SBA‐15 was investigated using Escherichia coli as an indicator bacterium, and the antimicrobial mechanism was explored. The properties and Ag+ release behaviour of Ag/SBA‐15 materials were compared. Experimental results showed that Ag/SBA‐15 materials resulted in 7·5 log inactivation of E. coli for only 60 min, which exhibited very high antimicrobial activities at room temperature without using any light or electrical power input. The cell wall and cell membrane were destroyed in the antimicrobial process, leading to leakage of intracellular components. The formation of extracellular reactive oxygen species (ROS) involved in the bactericidal process was confirmed. Production of intracellular ROS was also discovered.Conclusions Ag/SBA‐15 exhibited high antimicrobial activity against E. coli. This antimicrobial effect was a synergistic action between extracellular ROS and the toxicity of Ag+, which induced intracellular ROS production and subsequent cell death.Significance and Impact of the StudyThis study revealed for the first time the antimicrobial activities and mechanisms of Ag/SBA‐15 materials prepared with different methods.

Toxicity, bioaccumulation and biomagnification of silver nanoparticles in green algae (Chlorella sp.), water flea (Moina macrocopa), blood worm (Chironomus spp.) and silver barb (Barbonymus gonionotus)

The toxicity, bioaccumulation and biomagnification of material containing silver nanoparticles were studied in a model food chain. Two forms of silver namely, Ag+ and nano Ag° particles (AgNPs) were examined for their toxicity effects on Chlorella sp., Moina macrocopa, Barbonymus gonionotus and Chironomus spp. The results showed that the toxicity order on the four organisms was free Ag+> AgNPs. For toxicity of Ag+, the EC5° (effective concentration) was 0.39±0.32 mg L-1 for Chlorella sp. and the LC5° (lethal concentration) of M. macrocopa, B. gonionotus and Chironomus spp. were 0.026±0.43 mg L-1, 0.057±1.15 mg L-1, and 0.042±0.19 mg L-1, respectively. For toxicity, the EC5° of AgNPs was 0.89±0.68 mg L-1 for Chlorella sp. and the LC5° of M. macrocopa, B. gonionotusand Chironomus spp. were 1.11±0.86 mg L-1, 1.76±0.19 mg L-1, and 1.08±1.21 mg L-1, respectively. The results of the bioaccumulation study indicated that the highest bioaccumulation factor (BAF) of Ag+ was 101.84 L g-1 in Chlorella sp. and the lowest BAF of AgNPs was 1.89 L g-1 in B. gonionotus. The food chain transfer of AgNPs occurred only from Chlorella sp. to M. macrocopa and there was no evidence of biomagnification from food sources to consumers in a simple tropical food chain.

The persistence and transformation of silver nanoparticles in littoral lake mesocosms monitored using various analytical techniques

Environmental context Silver nanoparticles discharged with municipal wastewater may contaminate surface waters and harm aquatic ecosystems. We applied several analytical techniques to investigate the persistence and transformation of silver nanoparticles in a natural lake environment, and show, through multiple lines of evidence, that they persisted in lake water for several weeks after addition. The nanoparticles were releasing silver ions through dissolution, but these toxic ions were likely binding with natural organic matter in the lake water. Abstract Silver nanoparticles (AgNPs) may be released into surface waters, where they can affect aquatic organisms. However, agglomeration, dissolution, surface modifications and chemical speciation are important processes that control the toxicity of AgNPs. The purpose of the study was to apply various methods for monitoring the persistence and transformation of AgNPs added to littoral lake mesocosms. Analysis of total Ag showed that the levels in the mesocosms declined rapidly in the first 12h after addition, followed by a slower rate of dissipation with a half-life (t1/2) of ~20 days. Analysis using single particle ICP-MS (spICP-MS) showed no evidence of extensive homo-agglomeration of AgNPs. The stability of AgNPs was likely due to the low ionic strength and high concentrations of humic-rich dissolved organic carbon (DOC) in the lake water. Analyses by spICP-MS, cloud point extraction (CPE) and asymmetric flow field flow fractionation coupled to ICP-MS (AF4-ICP-MS) all indicated that the concentrations of AgNP decreased over time, and the nanoparticles underwent dissolution. However, the concentrations of dissolved silver, which includes Ag+, were generally below detection limits when analysed by centrifugal ultrafiltration and spICP-MS. It is likely that the majority of free ions released by dissolution were complexing with natural organic material, such as DOC. An association with DOC would be expected to reduce the toxicity of Ag+ in natural waters. Overall, we were able to characterise AgNP transformations in natural waters at toxicologically relevant concentrations through the use of multiple analytical techniques that compensate for the limitations of the individual methods.