Influence of dissolved oxygen on aggregation kinetics of citrate-coated silver nanoparticles

Aggregation, an important environmental behavior of silver nanoparticles (AgNPs) influences their bioavailability and cytotoxicity. The work studied the influence of dissolved oxygen (DO) or the redox potential on the stability of AgNPs in aqueous environments. This study employed time-resolved dynamic light scattering (TR-DLS) to investigate the aggregation kinetics of citrate-coated AgNPs. Our results demonstrated that when DO was present, the aggregation rates became much faster (e.g., 3-8 times) than those without DO. The hydrodynamic sizes of AgNPs had a linear growth within the initial 4-6 h and after the linear growth, the hydrodynamic sizes became random for AgNPs in the presence of DO, whereas in the absence of DO the hydrodynamic sizes grew smoothly and steadily. Furthermore, the effects of primary particles sizes (20, 40, and 80 nm) and initial concentrations (300 and 600 μg/L) of AgNPs on aggregation kinetics were also investigated.     

Photocatalytic degradation of gaseous toluene over Ag-doping TiO₂ nanotube powder prepared by anodization coupled with impregnation method

In this work, Ag-doping TiO₂ nanotubes were prepared and employed as the photocatalyst for the degradation of toluene. The TiO₂ nanotube powder was produced by the rapid-breakdown potentiostatic anodization of Ti foil in chloride-containing electrolytes, and then doped with Ag through an incipient wetness impregnation method. The samples were characterized by scanning electron microscope, high-resolution transmission electron microscopy, X-ray diffraction, surface photovoltage measurements, X-ray photoelectron spectroscopy and N₂ adsorption. The nanotubular TiO₂ photocatalysts showed an outer diameter of approximately 40 nm, fine mesoporous structure and high specific surface area. The photocatalytic activity of Ag-doping TiO₂ nanotube powder was evaluated through photooxidation of gaseous toluene. The results indicated that the degradation efficiency of toluene could get 98% after 4 h reaction using the Ag-doping TiO₂ nanotubes as the photocatalyst under UV light illumination, which was higher than that of the pure TiO₂ nanotubes, Ag-doping P25 or P25. Benzaldehyde species could be observed during the photocatalytic oxidation monitored by in situ FTIR, and the formed benzaldehyde intermediate during reaction would be partially oxidized into CO₂ and H₂O.     

Effect of silver nanoparticles in crop plants Phaseolus radiatus and Sorghum bicolor: media effect on phytotoxicity

Understanding some adverse effects of nanoparticles in edible crop plants is a matter of importance because nanoparticles are often released into soil environments. We investigated the phytotoxicity of silver nanoparticles (AgNPs) on the important crop plants, Phaseolus radiatus and Sorghum bicolor. The silver nanoparticles were selected for this study because of their OECD designation as a priority nanomaterial. The toxicity and bioavailability of AgNPs in the crop plant species P. radiatus and S. bicolor were evaluated in both agar and soil media. The seedling growth of test species was adversely affected by exposure to AgNPs. We found evidence of nanoparticle uptake by plants using electron microscopic studies. In the agar tests, P. radiatus and S. bicolor showed a concentration dependent-growth inhibition effect. Measurements of the growth rate of P. radiatus were not affected in the soil studies by impediment within the concentrations tested herein. Bioavailability of nanoparticles was reduced in the soil, and the dissolved silver ion effect also differed in the soil as compared to the agar. The properties of nanoparticles have been shown to change in soil, so this phenomenon has been attributed to the reduced toxicity of AgNPs to plants in soil medium. The application of nanoparticles in soil is a matter of great importance to elucidate the terrestrial toxicity of nanoparticles.     

Transport of silver nanoparticles (AgNPs) in soil

The effect of soil properties on the transport of silver nanoparticles (AgNPs) was studied in a set of laboratory column experiments, using different combinations of size fractions of a Mediterranean sandy clay soil. The AgNPs with average size of ∼30 nm yielded a stable suspension in water with zeta potential of −39 mV. Early breakthrough of AgNPs in soil was observed in column transport experiments. AgNPs were found to have high mobility in soil with outlet relative concentrations ranging from 30% to 70%, depending on experimental conditions. AgNP mobility through the column decreased when the fraction of smaller soil aggregates was larger. The early breakthrough pattern was not observed for AgNPs in pure quartz columns nor for bromide tracer in soil columns, suggesting that early breakthrough is related to the nature of AgNP transport in natural soils. Micro-CT and image analysis used to investigate structural features of the soil, suggest that soil aggregate size strongly affects AgNP transport in natural soil. The retention of AgNPs in the soil column was reduced when humic acid was added to the leaching solution, while a lower flow rate (Darcy velocity of 0.17 cm/min versus 0.66 cm/min) resulted in higher retention of AgNPs in the soil. When soil residual chloride was exchanged by nitrate prior to column experiments, significantly improved mobility of AgNPs was observed in the soil column. These findings point to the importance of AgNP-soil chemical interactions as a retention mechanism, and demonstrate the need to employ natural soils rather than glass beads or quartz in representative experimental investigations.     

Toxicity of silver nanoparticles to rainbow trout: A toxicogenomic approach

Silver (Ag) nanoparticles are used as antimicrobial adjuvant in various products such as clothes and medical devices where the release of nano-Ag could contaminate the environment and harm wildlife. The purpose of this study was to examine the sublethal effects of nano-Ag and dissolved Ag on Oncorhynchus mykiss rainbow trout. Hepatic Ag contents and changes in gene expression were monitored to provide insights on bioavailability and mode of action of both forms of silver. Fish were exposed to increasing concentrations (0.06, 0.6 and 6 μg L⁻¹) of nano-Ag (20 nm) and silver nitrate (AgNO₃) for 96 h at 15 °C. A gene expression analysis was performed in the liver using a DNA microarray of 207 stress-related genes followed by a quantitative polymerase chain reaction on a selection of genes for validation. The biochemical markers consisted of the determination of labile zinc, metallothioneins, DNA strand breaks, lipid peroxidation (LPO) and vitellogenin-like proteins. The analysis of total Ag in the aquarium water revealed that nano-Ag was mostly aggregated, with 1% of the total Ag being dissolved. Nevertheless, hepatic Ag content was significantly increased in exposed fish. Indeed, dissolved Ag was significantly more bioavailable than nano-Ag only at the highest concentration with 38 ± 10 and 11 ± 3 ng Ag mg⁻¹ proteins for dissolved and nano-Ag respectively. Exposure to both forms of Ag led to significant changes in gene expression for 13% of tested gene targets. About 12% of genes responded specifically to nano-Ag, while 10% of total gene targets responded specifically to dissolved Ag. The levels of vitellogenin-like proteins and DNA strand breaks were significantly reduced by both forms of Ag, but DNA break levels were lower with nano-Ag and could not be explained by the presence of ionic Ag. Labile zinc and the oxidized fraction of metallothioneins were increased by both forms of Ag, but LPO was significantly induced by nano-Ag only. A discriminant function analysis revealed that the responses obtained by biochemical markers and a selection of ten target genes were able to discriminate completely (100%) the effects of both forms of Ag. Exposure to nano-Ag involved genes in inflammation and dissolved Ag involved oxidative stress and protein stability. Hence, the toxicity of Ag will differ depending on the presence of Ag nanoparticles and aggregates.     

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag–Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag–PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72 h in freshwater (500–600 μg L⁻¹) and seawater (1300–1500 μg L⁻¹), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag⁺ (1.1, 400 and 0.11 μg L⁻¹, respectively), Ag–Cit (3.0, 2380 and 0.15 μg L⁻¹, respectively) and Ag–PVP (19.5, 3690 and 2.0 μg L⁻¹, respectively) varied widely, with toxicity in the order Ag⁺ > Ag–Cit > Ag–PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag⁺ or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.     

Effects of silver nanoparticles with different dosing regimens and exposure media on artificial ecosystem

Due to the wide use of silver nanoparticles (AgNPs) in various fields, it is crucial to explore the potential negative impacts on the aquatic environment of AgNPs entering into the environment in different ways. In this study, comparative experiments were conducted to investigate the toxicological impacts of polyvinylpyrrolidone-coated silver nanoparticles (PVP-AgNPs) with two kinds of dosing regimens, continuous and one-time pulsed dosing, in different exposure media (deionized water and XiangJiang River water). There were a number of quite different experimental results (including 100% mortality of zebrafish, decline in the activity of enzymes, and lowest number and length of adventitious roots) in the one-time pulsed dosing regimen at high PVP-AgNP concentration exposure (HOE) compared to the three other treatments. Meanwhile, we determined that the concentration of leached silver ions from PVP-AgNPs was too low to play a role in zebrafish death. Those results showed that HOE led to a range of dramatic ecosystem impacts which were more destructive than those of other treatments. Moreover, compared with the continuous dosing regimen, despite the fact that higher toxicity was observed for HOE, there was little difference in the removal of total silver from the aquatic environment for the different dosing regimens. No obvious differences in ecological impacts were observed between different water columns under low concentration exposure. Overall, this work highlighted the fact that the toxicity of AgNPs was impacted by different dosing regimens in different exposure media, which may be helpful for assessments of ecological impacts on aquatic environments.     

北海银滩滨海旅游度假区海域环境质量分析

2014年3月至10月通过对北海银滩滨海旅游度假区海域环境质量状况的监视监测,采用年平均指数法进行年度综合等级评价,并根据统计分析结果对影响该度假区的主要原因进行分析。研究结果表明,北海银滩滨海旅游度假区的水质指数为4.3,达到良好及以上的天数占97%,水质状况优良;海面状况指数为4.7,海面环境状况极佳;平均休闲(观光)活动指数为4.4,适宜开展各项休闲娱乐活动的天数达到90%以上。该度假区海域环境质量状况总体优良,很适宜开展滨海休闲观光活动,其中部分时段不适宜开展的主要原因是天气不佳。     

石墨炉原子吸收光谱法测定土壤中银

建立了土壤样品中痕量银的石墨炉原子吸收光谱测定方法,优化了试验条件,标准曲线线性关系良好,当取样质量为0.25 g,定容体积为25 mL时,方法检出限为0.01 mg/kg.经标准样品验证,方法准确度符合土壤样品分析要求.