Transformation Of Silver Nanoparticles Research Articles

Roles of hemocyte subpopulations in silver nanoparticle transformation and toxicity in the oysters Crassostrea hongkongensis

Hemocytes are the main immune cells in bivalve mollusks and one of the sensitive targets for nanoparticle toxicity. Bivalve hemocytes consist of multiple functional heterogeneous cell types, but their different roles in immune system against foreign particles remain largely unknown. In order to clarify the different immune responses of hemocyte subpopulations to silver nanoparticles (AgNPs) and Ag ions, in this study, the Hong Kong oyster (Crassostrea hongkongensis) hemocytes were employed and separated into three subpopulations based on their cell size and granularity, including agranulocytes (R1), semigranulocytes (R2), and granulocytes (R3). We first demonstrated that AgNPs could rapidly enter into the oyster hemocytes within 3 h by phagocytosis process and resulted in different immune responses in hemocyte subpopulations. The most affected cell subtype by AgNPs was the granulocytes, followed by semigranulocytes, whereas agranulocytes were not affected following exposure to AgNPs. Interestingly, AgNPs induced the granule formation in semigranulocytes and further increased the proportion of granulocytes, whereas their ionic counterparts had no such effects on hemocyte composition, indicating the different detoxification mechanisms for nanoparticulate and ionic form. Following AgNP exposure, the dissolved Ag ions were accumulated in lysosomes and caused lysosomal dysfunction, indicating that lysosomes were the main targets for AgNP toxicity and the dissolved Ag ions were the main contributor of AgNP toxicity. Furthermore, AgNP exposure induced reactive oxygen production and impeded the lysosome function and phagocytosis in granulocytes, with impaired immunity system in oysters. Our study identified the different immune responses of oyster hemocyte subpopulations to AgNPs based on the in vitro short-term exposure assays, which may be applied to rapidly evaluate the ecotoxicological risks of different nanoparticles in aquatic systems.

Uptake, translocation, and transformation of silver nanoparticles in plants

This article reviews the plant uptake of silver nanoparticles (AgNPs) that occurred in soil systems and the in planta fate of Ag.

Transformation of Silver Nanoparticles (AgNPs) during Lime Treatment of Wastewater Sludge and Their Impact on Soil Bacteria.

This study investigated the impact of lime stabilization on the fate and transformation of AgNPs. It also evaluated the changes in the population and diversity of the five most relevant bacterial phyla in soil after applying lime-stabilized sludge containing AgNPs. The study was performed by spiking an environmentally relevant concentration of AgNPs (2 mg AgNPs/g TS) in sludge, applying lime stabilization to increase pH to above 12 for two hours, and applying lime-treated sludge to soil samples. Transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS) were used to investigate the morphological and compositional changes of AgNPs during lime stabilization. After the application of lime stabilized sludge to the soil, soil samples were periodically analyzed for total genomic DNA and changes in bacterial phyla diversity using quantitative polymerase chain reaction (qPCR). The results showed that lime treatment effectively removed AgNPs from the aqueous phase, and AgNPs were deposited on the lime molecules. The results revealed that AgNPs did not significantly impact the presence and diversity of the assessed phyla in the soil. However, lime stabilized sludge with AgNPs affected the abundance of each phylum over time. No significant effects on the soil total organic carbon (TOC), heterotrophic plate count (HPC), and percentage of the live cells were observed.

Toxicity, bioaccumulation, and transformation of silver nanoparticles in aqua biota: a review

Toxicity, bioaccumulation, and transformation of silver nanoparticles in aqua biota: a review

Fate and transformation of silver nanoparticles in different biological conditions.

The exploitation of silver nanoparticles (AgNPs) in biomedicine represents more than one third of their overall application. Despite their wide use and significant amount of scientific data on their effects on biological systems, detailed insight into their in vivo fate is still lacking. This study aimed to elucidate the biotransformation patterns of AgNPs following oral administration. Colloidal stability, biochemical transformation, dissolution, and degradation behaviour of different types of AgNPs were evaluated in systems modelled to represent biological environments relevant for oral administration, as well as in cell culture media and tissue compartments obtained from animal models. A multimethod approach was employed by implementing light scattering (dynamic and electrophoretic) techniques, spectroscopy (UV–vis, atomic absorption, nuclear magnetic resonance) and transmission electron microscopy. The obtained results demonstrated that AgNPs may transform very quickly during their journey through different biological conditions. They are able to degrade to an ionic form and again reconstruct to a nanoparticulate form, depending on the biological environment determined by specific body compartments. As suggested for other inorganic nanoparticles by other research groups, AgNPs fail to preserve their specific integrity in in vivo settings.

Subcellular Imaging of Localization and Transformation of Silver Nanoparticles in the Oyster Larvae.

To accurately assess the behavior and toxicity of silver nanoparticles (AgNPs), it is essential to understand their subcellular distribution and biotransformation. We combined both nanoscale secondary ion mass spectrometry (NanoSIMS) and electron microscopy to investigate the subcellular localization of Ag and in situ chemical distribution in the oyster larvae Crassostrea angulata after exposure to isotopically enriched 109AgNPs. Oyster larvae directly ingested particulate Ag, and in vivo dissolution of AgNPs occurred. The results collectively showed that AgNPs were much less bioavailable than Ag+, and the intracellular Ag was mainly originated from the soluble Ag, especially those dissolved from the ingested AgNPs. AgNPs absorbed on the cell membranes continued to release Ag ions, forming inorganic Ag-S complexes extracellularly, while Ag-organosulfur complexes were predominantly formed intracellularly. The internalized Ag could bind to the sulfur-rich molecules (S-donors) in the cytosol and/or be sequestered in the lysosomes of velum, esophagus, and stomach cells, as well as in the digestive vacuoles of digestive cells, which could act as a detoxification pathway for the oyster larvae. Ag was also occasionally incorporated into the phosphate granules, rough endoplasmic reticulum, and mitochondria. Our work provided definite evidence for the partial sulfidation of AgNPs after interaction with oyster larvae and shed new light on the bioavailability and fate of nanoparticles in marine environment.

Transformation of silver nanoparticles in coagulation processes and subsequent thermal sludge treatments

Abstract Increased use of silver nanoparticles (AgNPs) in commercial products inevitably leads to their release into the environment through sludge discharge from wastewater treatment facilities. The silver morphology and speciation in sludge plays an important role in the biotoxicity and subsequent risk assessment of AgNPs. In this study, we investigated the morphology and speciation of AgNPs after coagulation and subsequent sludge thermal treatment, treated simulated water samples that were prepared with bare and macromolecule polymers (PVP) coated AgNPs. Results from X-ray photoelectron spectroscopy and X-ray diffraction analysis demonstrated that bare AgNPs, which aggregated to large sizes before coagulation, existed as crystalline metallic silver (68.8%) and argentic chloride (31.2%) in flocs. As bare AgNPs flocs were calcinated at 600 °C, part of the metallic silver transferred to silver oxide (Ag2O). Analysis of Ag fractions showed that the percentages of dissolved silver and nano silver in bare AgNPs flocs increased drastically over 30% in acidic conditions or in the presence of calcium ions and humic acid, and further increased after calcination. In comparison, most of the PVP coated AgNPs were immobilized in flocs as Ag2O and argentic chloride. The sludge calcination did not produce any further modification in silver speciation. Comparison of the results between bare and PVP coated AgNPs demonstrated that nanoparticle aggregation before treatment is not conducive to immobilization of AgNPs in flocs, and results in health hazards and ecological risks due to the release of silver.

Concentration dependent effect of humic acid on the transformations of silver nanoparticles

Influence of humic acid (HA) concentration on the colloidal stability and dissolution of silver nanoparticles (AgNPs) was evaluated in a series of long-term experiments. The stability of freshly synthesized and uncoated AgNPs was investigated as a function of HA concentration (0–250 mg/L). In the absence of HA, AgNPs underwent oxidative dissolution and aggregation disturbing the colloidal stability of AgNPs. In the HA concentration range of 1–20 mg/L, HA stabilized AgNPs due to the inhibition of the release of ionic Ag ensuring the persistence of AgNPs in the aquatic environment for a longer period. At higher concentrations of HA (20–250 mg/L) in the soil environment, AgNPs were wrapped by the HA molecules, increasing the hydrodynamic diameter of the AgNPs. Due to the suppression of dissolution of AgNPs, primary particles remained stable in the environment for a prolonged period with no change in the primary particle size and morphology. Furthermore, it was observed that ionic Ag in the solution can be reduced to form fresh, secondary AgNPs at the lower levels of HA in the aquatic environment, in the presence of sunlight. This study is important in understanding the role of HA on the stability of AgNPs in the natural environment.

Uptake and Transformation of Silver Nanoparticles and Ions by Rice Plants Revealed by Dual Stable Isotope Tracing.

Knowledge on the uptake and transformation of silver nanoparticles (AgNPs) and Ag+ ions by organisms is critical for understanding their toxicity. Herein, the differential uptake, transformation, and translocation of AgNPs and Ag+ ions in hydroponic rice ( Oryza sativa L.) is assessed in modified Hewitt (with Cl- ions, HS(Cl)) and Hogland solutions (without Cl- ions, HS) using dual stable isotope tracing (107AgNO3 and 109AgNPs). After coexposure to 107Ag+ ions and 109AgNPs at 50 μg L-1 (as Ag for both) for 14 days, a stimulatory effect was observed on root elongation (increased by 68.8 and 71.9% for HS(Cl) and HS, respectively). Most of the Ag+ ions (from 107Ag+ ions and 109AgNPs) were retained on the root surface, while the occurrence of AgNPs (from 109AgNPs and 107Ag+ ions) was observed in the root, suggesting the direct uptake of AgNPs and/or reduction of Ag+ ions. Higher fractions of Ag+ ions in the shoot suggest an in vivo oxidation of AgNPs. These results demonstrated the intertransformation between Ag+ ions and AgNPs and the role of AgNPs as carriers and sources of Ag+ ions in organisms, which is helpful for understanding the fate and toxicology of Ag.

Impacts of titanium dioxide nanoparticles on transformation of silver nanoparticles in aquatic environments

Under sunlight irradiation, titanium dioxide nanoparticles could promote the oxidative dissolution of silver nanoparticles in aquatic environments.

Mechanism of toxicity and transformation of silver nanoparticles: Inclusive assessment in earthworm-microbe-soil-plant system

Long term and inclusive toxicity studies encompassing soil, plants, and organisms are rare in literature for AgNPs. This study examines AgNP behavior in soil-plant system through 72weeks long soil experiment, earthworm response, and plant metabolic analysis. AgNP exposed earthworms did not show reproductive failure; yet high oxidative stress and reduced protein synthesis led to significant weight loss. Such stress was highest with AgNP50 exposure. Correspondingly, the 50ppm exposure of AgNP was capable to reduce nutrient availability and microbial growth in soil. Contrary to previous reports, we demonstrated that dissolution rate of AgNP increased with time in soil. Dynamic Light Scattering and UV-VIS assessments exhibited concentration and time dependent agglomeration of AgNP in soil and aqueous media. Moreover, lab based experiments in aqueous medium revealed that significant reduction in silver availability was due to formation of Ag2S or Ag3PO4; which also greatly affected the P and S availability. Although the vegetative growth of tomato was normal, AgNP (10mgkg−1) treatment markedly upset the fruit yield. The 10mgkg−1 AgNP exposure significantly enhanced oxidative stress and Ag uptake in plants; consequently, retarded N-assimilating enzyme (glutamate synthase, glutamine synthetase, and nitrate reductase) activity by suppressing their genes in plants. Eventually, photosynthesis and CO2 assimilating efficiency were severely disrupted. These assays were vital to appreciate the true toxicity and are not well attended in most of the studies with AgNPs.

Natural formation and transformation of silver nanoparticles in the aquatic environment

Silver nanoparticles (AgNPs) are well known for their excellent antibacterial ability and superior physiochemical properties, and are widely used in a growing number of applications, including home disinfectants, medical devices and water purificants. During the production, use and disposal of AgNP-containing products, AgNPs may be released into the environment. AgNPs are highly dynamic in aqueous systems. They could undergo different chemical and morphology transformation, which greatly affects their final fate, transport, distribution and potential bioeffects. The study on the fate and transformation of AgNPs in natural systems is the basis and prerequisite for the accurate assessment of environmental and biological safety of AgNPs. Herein, we reviewed the recent progress of the natural formation and transformation of AgNPs in the aquatic environment, including the chemical and biosynthesis of AgNPs, the aggregation, enrichment in water surface microlayer, oxidation and dissolution, sulfidation and chlorination of AgNPs in the aquatic environment. The prospects and possible directions in the field are also discussed.

Transformations of silver nanoparticles in wastewater effluents: links to Ag bioavailability

Physicochemical modifications of silver nanoparticles in wastewaters determine their bioavailability toChlamydomonas reinhardtii.

Monitoring the Fate and Transformation of Silver Nanoparticles in Natural Waters.

There is potential for silver nanoparticles (AgNPs) to be released into surface waters and thus affect aquatic organisms. However, agglomeration, dissolution, surface modifications and chemical speciation are important transformation processes that control the toxicity of AgNPs. Analytical methods are needed to determine the size distribution, mass and form of AgNPs and other silver species in natural waters. Cloud point extraction, single particle inductively coupled plasma mass spectrometry (spICP-MS) and asymmetric flow field flow fractionation with on-line ICP-MS (AF4-ICP-MS) are analytical techniques that show potential for quantitative analysis of AgNPs in aquatic matrices at environmentally relevant concentrations. In this review, we discuss the fate processes for AgNPs in natural waters and the analytical methods that can be used to determine the distribution of AgNPs and their transformation products.

Transformation of Silver Nanoparticles in Sewage Sludge during Incineration.

Silver nanoparticles (Ag-NP) discharged into the municipal sewer system largely accumulate in the sewage sludge. Incineration and agricultural use are currently the most important strategies for sewage sludge management. Thus, the behavior of Ag-NP during sewage sludge incineration is essential for a comprehensive life cycle analysis and a more complete understanding of the fate of Ag-NP in the (urban) environment. To address the transformation of Ag-NP during sewage sludge incineration, we spiked metallic Ag(0)-NP to a pilot wastewater treatment plant and digested the sludge anaerobically. The sludge was then incinerated on a bench-scale fluidized bed reactor in a series of experiments under variable conditions. Complementary results from X-ray absorption spectroscopy (XAS) and electron microscopy-energy dispersive X-ray (EM-EDX) analysis revealed that Ag(0)-NP transformed into Ag2S-NP during the wastewater treatment, in agreement with previous studies. On the basis of a principal component analysis and subsequent target testing of the XAS spectra, Ag(0) was identified as a major Ag component in the ashes, and Ag2S was clearly absent. The reformation of Ag(0)-NP was confirmed by EM-EDX. The fraction of Ag(0) of the total Ag in the ashes was quantified by linear combination fitting (LCF) of XAS spectra, and values as high as 0.8 were found for sewage sludge incinerated at 800 °C in a synthetic flue gas atmosphere. Low LCF totals (72% to 94%) indicated that at least one relevant reference spectrum was missing in the LCF analysis. The presence of spherical Ag-NP with a diameter of <50 nm extending into the sub-nm range was revealed by electron microscopy analyses. The rapid formation of Ag(0)-NP from Ag2S during sewage sludge incineration, as demonstrated in this study, needs to be considered in the life cycle assessment of engineered Ag-NP.

High Resolution STEM-EELS Study of Silver Nanoparticles Exposed to Light and Humic Substances.

Nanoparticles (NPs) are defined as particles with at least one dimension between 1 and 100 nm or with properties that differ from their bulk material, which possess unique properties. The extensive use of NPs means that discharge to the environment is likely increasing, but fate, behavior, and effects under environmentally relevant conditions are insufficiently studied. This paper focuses on the transformations of silver nanoparticles (AgNPs) under simulated but realistic environmental conditions. High resolution aberration-corrected scanning transmission electron microscopy (HAADF STEM) coupled with electron energy loss spectroscopy (EELS) and UV-vis were used within a multimethod approach to study morphology, surface chemistry transformations, and corona formation. Although loss, most likely by dissolution, was observed, there was no direct evidence of oxidation from the STEM-EELS. However, in the presence of fulvic acid (FA), a 1.3 nm oxygen-containing corona was observed around the AgNPs in water; modeled data based on the HAADF signal at near atomic resolution suggest this was an FA corona was formed and was not silver oxide, which was coherent (i.e., fully coated in FA), where observed. The corona further colloidally stabilized the NPs for periods of weeks to months, dependent on the solution conditions.

Timescale of silver nanoparticle transformation in neural cell cultures impacts measured cell response

Both serum protein concentration and ionic strength are important factors in nanoparticle transformation within cell culture environments. However, silver nanoparticles are not routinely tracked at their working concentration in the specific medium used for in vitro toxicology studies. Here we evaluated the transformation of electrostatically stabilized citrate nanoparticles (C-AgNPs) and sterically stabilized polyvinylpyrrolidone nanoparticles (PVP-AgNPs) in a low-serum (~ 0.2 mg/mL bovine serum albumin) culture medium, while measuring the response of rat cortex neural progenitor cells, which differentiate in this culture environment. After 24 h, silver nanoparticles at concentrations up to 10 µg/mL did not affect adenosine triphosphate levels, whereas silver ions decreased adenosine triphosphate levels at concentrations of 1.1 µg/mL or higher. After 240 h, both silver nanoparticles, as well as silver ion, unambiguously decreased adenosine triphosphate levels at concentrations of 1 and 1.1 µg/mL, respectively, suggesting particle dissolution. Particle transformation was investigated in 1:10 diluted, 1:2 diluted, or undiluted differentiation medium, all having an identical protein concentration, to separate the effect of serum protein stabilization from ionic strength destabilization. Transmission electron microscopy images indicated that particles in 1:10 medium were not surrounded by proteins, whereas particles became clustered within a non-crystalline protein matrix after 24 h in 1:2 medium and at 0 h in undiluted medium. Despite evidence for a protein corona, particles were rapidly destabilized by high ionic strength media. Polyvinylpyrrolidone increased the stability of singly dispersed particles compared to citrate ligands; however, differences were negligible after 4 h in 1:2 medium or after 1 h in undiluted medium. Thus low-serum culture environments do not provide sufficient colloidal stability for long-term toxicology studies with citrate- or polyvinylpyrrolidone-stabilized silver nanoparticles.

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.

Optimized Synthetic Protocols for Preparation of Versatile Plasmonic Platform Based on Silver Nanoparticles with Pentagonal Symmetries

The key findings in the synthesis and transformation of silver nanoparticles with pentagonal symmetries arising from regular multiple twinning are reported, researched in the last 5 years. In a one‐stage photochemical synthesis of silver decahedral (pentagonal bipyramid, J13 solid) nanoparticles (AgDeNPs), oxidative etching by hydrogen peroxide is implemented to achieve complete conversion of the small silver platelet precursor NPs. The concentration of hydrogen peroxide is found to be optimal at 0.2 m. Such high peroxide concentration can be rationalized by its slow reactivity in a red‐ox equilibrium with borohydride and citrate. We have also adapted light‐emitting diodes (LEDs) as a light source and documented optimal exposure time, LED power, and wavelength range for convenient laboratory synthesis of high‐purity size‐selected AgDeNPs. In the absence of platelet impurities, AgDeNPs produce by the new‐generation procedure can be conveniently re‐grown into larger sizes using silver ions as a precursor. Thermal regrowth of new‐generation AgDeNPs into pentagonal silver nanorods (AgPRNPs, J15 solid) can be reliably accomplished with the precise variation in rod length (by varying amounts of added silver) and width (by using different seed AgDeNPs). With the reported reproducible synthetic protocols that can be readily implemented in any chemistry laboratory, AgDeNPs and AgPRNPs should serve as a versatile plasmonic platform with a precisely tunable surface plasmon resonance (SPR) from ca. 430 nm (rounded AgDeNPs) to 1100+ nm (longitudinal SPR of longer AgPRNPs). The plasmonic platform based on the reported AgNPs with pentagonal symmetries should be practical for a diverse range of applications, especially plasmonic sensing and surface‐enhanced Raman spectroscopy.

Nanosilver: Weighing the Risks and Benefits

It takes a special sort of case to spur attorneys into a debate over the drooling habits of toddlers. Yet that’s where lawyers from the Natural Resources Defense Council (NRDC), the U.S. Environmental Protection Agency (EPA), and Swiss chemicals company HeiQ found themselves in January 2013 as they debated in a federal appeals court the extent to which 1-year-olds and 3-year-olds chew, salivate, and swallow.1 At issue in the NRDC’s suit against the EPA, which is still awaiting ruling, was whether the agency was right in granting a conditional registration in December 2011 to a nanosilver-based antimicrobial fabric treatment manufactured by HeiQ.2 The EPA’s risk assessment was based in part on assumptions about exposure of 3-year-olds by sucking or chewing on nanosilver-laced textiles such as clothing, blankets, and pillowcases. Silver nanoparticles are added to a variety of textiles and home goods as an antimicrobial. Although silver has been used safely for centuries, some question whether the rapid expansion of new exposure sources to nanosilver could have adverse consequences. ... NRDC lawyer Catherine Rahm, however, begged to differ with the agency’s methods. In the January hearing, she argued that the agency record shows infants are more likely than any other subset of children to chew on fabrics that could contain the pesticide, and that if the agency were to recalculate its risk assessment based on the body weight of a 1-year-old, nanosilver concentrations in HeiQ’s product could result in potentially harmful exposures. It’s an obscure but critical distinction as far as risk assessment goes. And given the implications for HeiQ and other companies looking to follow in its footsteps, the case has landed at the center of a prolonged conflict over the regulation of nanosilver and the growing deployment of this antimicrobial ingredient in a variety of commercial and consumer products. Yet regardless of which side prevails in the case, the truth about nanosilver is not black and white. Even the loudest voices joining the NRDC’s call for strict regulation of nanosilver concede that context is key. “I’m not somebody who is for or against nano,” says Ian Illuminato, who directs Friends of the Earth’s U.S. nanotechnology campaign, which has produced a series of reports on the potential dangers of nanosilver and other nanomaterials. “I’m just saying we need to do this in a mature and adult way. That’s not to say this isn’t a helpful technology and it doesn’t have a place in our future, but in the way it’s evolving right now, it’s very risky.” Greg Lowry, a researcher at Carnegie Mellon University who studies the fate of nanoparticles in the environment, agrees that the use of nanosilver is a matter of balancing risk and reward. “There’s a tremendous potential benefit to the use in some of these products,” he says. “What one has to do is to ask yourself whether the benefits outweigh the risk.”