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 8 hr-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.     

Interactions between engineered nanoparticles and dissolved organic matter: A review on mechanisms and environmental effects

Dissolved organic matter (DOM) is ubiquitous in the environment and has high reactivity. Once engineered nanoparticles (ENPs) are released into natural systems, interactions of DOM with ENPs may significantly affect the fate and transport of ENPs, as well as the bioavailability and toxicity of ENPs to organisms. However, because of the complexity of DOM and the shortage of useful characterization methods, large knowledge gaps exist in our understanding of the interactions between DOM and ENPs. In this article, we systematically reviewed the interactions between DOM and ENPs, discussed the effects of DOM on the environmental behavior of ENPs, and described the changes in bioavailability and toxicity of ENPs caused by DOM. Critical evaluations of published references suggest further need for assessing and predicting the influences of DOM on the transport, transformation, bioavailability, and toxicity of ENPs in the environment.     

Comparative toxicity of silver nanoparticles and silver ions to Escherichia coli

With the increase in silver(Ag)-based products in our lives, it is essential to test the potential toxicity of silver nanoparticles(Ag NPs) and silver ions(Ag ions) on living organisms under various conditions. Here, we investigated the toxicity of Ag NPs with Ag ions to Escherichia coli K-12 strain under various conditions. We observed that both Ag NPs and Ag ions display antibacterial activities, and that Ag ions had higher toxicity to E. coli K-12 strain than Ag NPs under the same concentrations. To understand the toxicity of Ag NPs at a cellular level, reactive oxygen species(ROS) enzymes were detected for use as antioxidant enzymatic biomarkers. We have also studied the toxicity of Ag NPs and Ag ions under various coexistence conditions including: fixed total concentration, with a varied the ratio of Ag NPs to Ag ions; fixed the Ag NPs concentration and then increased the Ag ions concentration; fixed Ag ions concentration and then increasing the Ag NPs concentration.Exposure to Ag NPs and Ag ions clearly had synergistic toxicity; however, decreased toxicity(for a fixed Ag NPs concentration of 5 mg/L, after increasing the Ag ions concentration) to E. coli K-12 strain. Ag NPs and Ag ions in the presence of L-cysteine accelerated the bacterial cell growth rate, thereby reducing the bioavailability of Ag ions released from Ag NPs under the single and coexistence conditions. Further works are needed to consider this potential for Ag NPs and Ag ions toxicity across a range of environmental conditions.Environmental Significance Statement: As silver nanoparticles(Ag NPs)-based products are being broadly used in commercial industries, an ecotoxicological understanding of the Ag NPs being released into the environment should be further considered. Here, we investigate the comparative toxicity of Ag NPs and silver ions(Ag ions) to Escherichia coli K-12 strain, a representative ecotoxicological bioreporter. This study showed that toxicities of Ag NPs and Ag ions to E. coli K-12 strain display different relationships when existing individually or when coexisting, and in the presence of L-cysteine materials. These findings suggest that the toxicology research of nanomaterials should consider conditions when NPs coexist with and without their bioavailable ions.     

Complex interplay between formation routes and natural organic matter modification controls capabilities of C60 nanoparticles (nC60) to accumulate organic contaminants

Accumulation of organic contaminants on fullerene nanoparticles (nC₆₀) may significantly affect the risks of C₆₀ in the environment. The objective of this study was to further understand how the interplay of nC₆₀ formation routes and humic acid modification affects contaminant adsorption of nC₆₀. Specifically, adsorption of 1,2,4,5-tetrachlorobenzene (a model nonionic, hydrophobic organic contaminant) on nC₆₀ was greatly affected by nC₆₀ formation route – the formation route significantly affected the aggregation properties of nC₆₀, thus affecting the available surface area and the extent of adsorption via the pore-filling mechanism. Depending on whether nC₆₀ was formed via the “top-down” route (i.e., sonicating C₆₀ powder in aqueous solution) or “bottom-up” route (i.e., phase transfer from an organic solvent) and the type of solvent involved (toluene versus tetrahydrofuran), modification of nC₆₀ with Suwannee River humic acid (SRHA) could either enhance or inhibit the adsorption affinity of nC₆₀. The net effect depended on the specific way in which SRHA interacted with C₆₀ monomers and/or C₆₀ aggregates of different sizes and morphology, which determined the relative importance of enhanced adsorption from SRHA modification via preventing C₆₀ aggregation and inhibited adsorption through blocking available adsorption sites. The findings further demonstrate the complex mechanisms controlling interactions between nC₆₀ and organic contaminants, and may have significant implications for the life-cycle analysis and risk assessment of C₆₀.     

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.     

Characterization of natural organic matter in water for optimizing water treatment and minimizing disinfection by-product formation

正Introduction Natural organic matter(NOM)present in source water has significant impact on water treatment processes and on the quality of drinking water.NOM is a complex mixture of diverse groups of organic compounds,humic and fulvic acids,proteins,peptides,carbohydrates,and heterogeneous materials     

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV–visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV–visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca^2 + and Mg^2 +) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments.     

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO₂NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO₂NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO₂NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO₂NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO₂NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO₂NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.     

A critical review of the influence of effluent irrigation on the fate of pesticides in soil

The impact of effluent irrigation on the transformation and mobility of organic contaminants is poorly understood. The objectives of this review paper are: (i) to discuss the fundamental processes influencing the transformation and transport of pesticides in soil; (ii) to present a critical analysis of the impact of effluent irrigation on the transformation and transport of pesticides in soils; (iii) to suggest research areas that need attention. Effluent irrigation affects the fate of pesticides through its direct effect on the transformation and transport of pesticides that are already present at the irrigation sites, and its indirect effect on soil properties that are important in controlling the transformation and transport of organic contaminants. It has often been noticed that the effluent-derived dissolved organic matter (DOM) facilitates the movement of soil-borne pesticides by forming soluble pesticide complexes, and enhances their biodegradation by providing energy sources for the microorganisms that are involved in pesticide degradation. However, the results of field and laboratory experiments that examined the effect of effluent irrigation on the fate of pesticides are inconsistent; in some cases reduced mobility resulting from enhanced pesticide sorption has been observed, but enhanced pesticide mobility has also been reported. The inconsistency may be related to the inherent spatial variability of soil properties and/or the heterogeneity of effluent quality. For example, effluents vary in the nature and concentration of DOM that play a vital role in the degradation, sorption and transport behaviour of pesticides. Similarly, they vary in the concentrations of solvents and surfactants that have been shown to impact sorption and transport of organic contaminants. Field-based investigations on the impact of effluent irrigation on pesticide fate coupled with an accurate characterisation of the effluent are urgently required to assess the long-term risk associated with effluent irrigation in relation to pesticide transformation and transport.     

Green synthesis, characterization and antimicrobial activity of silver nanoparticles using methanolic root extracts of Diospyros sylvatica

The current research study focuses to formulate the biosynthesized silver nanoparticles for the first time from silver acetate using methanolic root extracts of Diospyros sylvatica, a member of family Ebenaceae. TEM analysis revealed the average diameter of Ag NPs around 8 nm which is in good agreement with the average crystallite size (10 nm) calculated from X-ray Diffraction (XRD) analysis. Further the study has been extended to the antimicrobial activity against test pathogenic Gram (+) ve, Gram (−) ve bacterial and fungal strains. The bioinspired Ag-NP showed promising activity against all the tested bacterial strains and the activity was enhanced with increased dosage levels.     

小麦对纳米银的吸收及毒性响应

以纳米银（AgNPs）为研究对象,Ag⁺（AgNO₃）为对照,通过添加半胱氨酸（L-cysteine）探讨小麦对AgNPs的吸收累积和毒性响应.小麦幼苗于不同浓度的AgNPs悬浮液中培养4h后,根系出现氧化应激反应和细胞膜损伤,丙二醛（MDA）和过氧化氢酶（CAT）含量分别由对照组的（2.9±0.5）nmol/L/mgprot和（8.6±1.2）U/mgprot增加至（4.9±1.5）nmol/L/mgprot和（12.4±1.2）U/mgprot.半胱氨酸缓解了AgNO₃对小麦的毒性并使小麦对AgNO₃的吸收速率常数从（275.4±12.3）L/（kg×h）降低到（210.8±11.2）L/（kg×h）.然而,半胱氨酸并没有缓解AgNPs对小麦的毒性,且AgNPs的吸收速率常数没有显著性变化[（12.6±0.8）和（11.2±0.6）L/（kg×h）].这说明AgNPs对小麦的有效性和毒性不仅来源于其释放的Ag⁺,还来源于纳米颗粒本身.通过进一步计算AgNPs暴露液中不同形态Ag的吸收速率常数,发现Ag⁺吸收速率常数最高[（275.4±12.3）L/（kg×h）],Ag-cysteine络合物吸收速率常数次之[（210.8±11.2）L/（kg×h）],纳米颗粒吸收速率常数最低[1.6L/（kg×h）].实验中建立了吸收速率常数预测方程,该方程预测结果与实验观测结果一致,说明该方程能够较好地描述小麦吸收AgNPs的具体过程.     

Molecular toxicity and defense mechanisms induced by silver nanoparticles in Drosophila melanogaster

The widely use of silver nanoparticles (AgNPs) as antimicrobial agents gives rise to potential environmental risks. AgNPs exposure have been reported to cause toxicity in animals. Nevertheless, the known mechanisms of AgNPs toxicity are still limited. In this study, we systematically investigated the toxicity of AgNPs exposure using Drosophila melanogaster. We show here that AgNPs significantly decreased Drosophila fecundity, the third-instar larvae weight and rates of pupation and eclosion in a dose-dependent manner. AgNPs reduced fat body cell viability in MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assays. AgNPs caused DNA damage in hemocytes and S2 cells. Interestingly, the mRNA levels of the entire metallothionein gene family were increased under AgNPs exposure as determined by RNA-seq analysis and validated by qRT-PCR, indicating that Drosophila responded to the metal toxicity of AgNPs by producing metallothioneins for detoxification. These findings provide a better understanding of the mechanisms of AgNPs toxicity and may provide clues to effect on other organisms, including humans.     

臭氧预氧化对芘在天然有机物中分配行为的影响

以疏水性有机物——芘为代表,考察了臭氧预氧化处理对高稳定性有机污染物在天然有机物(NOM)中分配行为的影响.结果表明,芘在不同性质NOM中分配系数(K_oc)的大小与NOM中芳香结构和疏水基团含量有关,芘在液相、吸附相NOM中的分配行为受NOM自身特性、吸附性能及吸附剂表面有机碳覆盖率(f_oc)大小的影响.臭氧预氧化能够破坏NOM中的芳香结构和疏水结构,削弱NOM与芘之间的相互作用,降低芘的Koc,臭氧预氧化对吸附相NOM疏水结构的破坏是造成芘在吸附相NOM中分配能力降低的主要原因.     

纳米银对聚磷菌吸磷和释磷的影响及毒性效应

利用硼氢化钠还原硝酸银,并使用聚乙烯醇（PVA）作为分散剂,制备出分散良好、粒径为（14±3）nm的纳米银颗粒,考察了其对聚磷菌（Microlunatus phosphovorus）好氧吸磷和厌氧释磷的影响,以及产生的毒性效应.结果表明,在好氧状态下,7mg/L的纳米银能够完全抑制聚磷菌的生长（P <0.01）,达到10mg/L时才能完全抑制聚磷菌的吸磷能力（P=0.01）;在厌氧状态下,大于20mg/L的纳米银才使聚磷菌释磷能力受到部分抑制（P <0.05）.活性氧簇（ROS）和扫描电子显微镜（SEM）的检测结果表明,纳米银使细菌体内ROS水平降低,部分细菌菌体表面塌陷,这说明,纳米银不但可以毒害聚磷菌菌体表面,还可以降低菌内ROS水平.     

Interaction of silver nanoparticles with mediterranean agricultural soils: Lab-controlled adsorption and desorption studies

The production of silver nanoparticles (AgNPs) has increased tremendously during recent years due to their antibacterial and physicochemical properties. As a consequence, these particles are released inevitably into the environment, with soil being the main sink of disposal. Soil interactions have an effect on AgNP mobility, transport and bioavailability. To understand AgNP adsorption processes, lab-controlled kinetic studies were performed. Batch tests performed with five different Mediterranean agricultural soils showed that cation exchange capacity and electrical conductivity are the main parameters controlling the adsorption processes. The adsorption kinetics of different sized (40, 75, 100 and 200?nm) and coated (citrate, polyvinylpyrrolidone and polyethyleneglycol (PEG)) AgNPs indicated that these nanoparticle properties have also an effect on the adsorption processes. To assess the mobility and bioavailability of AgNPs and to determine if their form is maintained during adsorption/desorption processes, loaded soils were submitted to leaching tests three weeks after batch adsorption studies. The DIN 38414-S4 extraction method indicated that AgNPs were strongly retained on soils, and single-particle inductively coupled plasma mass spectrometry confirmed that silver particles maintained their nanoform, except for 100?nm PEG-AgNPs and 40?nm citrate-coated AgNPs. The DTPA (diethylenetriaminepentaacetic acid) leaching test was more effective in extracting silver, but there was no presence of AgNPs in almost all of these leachates.     

Application of nanoparticle tracking analysis for characterising the fate of engineered nanoparticles in sediment-water systems

Novel applications of nanotechnology may lead to the release of engineered nanoparticles (ENPs), which result in concerns over their potential environmental hazardous impact. It is essential for the research workers to be able to quantitatively characterise ENPs in the environment and subsequently to assist the risk assessment of the ENPs. This study hence explored the application of nanoparticle tracking system (NTA) to quantitatively describe the behaviour of the ENPs in natural sediment-water systems. The NTA allows the measurement of both particle number concentration (PNC) and particle size distribution (PSD) of the ENPs. The developed NTA method was applied to a range of gold and magnetite ENPs with a selection of surface properties. The results showed that the positively-charged ENPs interacted more strongly with the sediment than neutral and negatively-charged ENPs. It was also found that the citrate coated Au ENPs had a higher distribution percentage (53%) than 11-mercaptoundecanoic acid coated Au ENPs (20%) and citrate coated magnetite ENPs (21%). The principles of the electrostatic interactions between hard (and soft) acids and bases (HSAB) are used to explain such behaviours; the hard base coating (i.e. citrate ions) will interact more strongly with hard acid (i.e. magnetite) than soft acid (i.e. gold). The results indicate that NTA is a complementary method to existing approaches to characterise the fate and behaviour of ENPs in natural sediment.     

Molecular characterization of effluent organic matter in secondary effluent and reclaimed water: Comparison to natural organic matter in source water

Municipal wastewater reclamation is becoming of increasing importance in the world to solve the problem of water scarcity. A better understanding of the molecular composition of effluent organic matter(Ef OM) in the treated effluents of municipal wastewater treatment plants(WWTPs) is crucial for ensuring the safety of water reuse. In this study, the molecular composition of Ef OM in the secondary effluent of a WWTP in Beijing and the reclaimed water further treated with a coagulation–sedimentation–ozonation process were characterized using a non-target Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) method and compared to that of natural organic matter(NOM) in the local source water from a reservoir. It was found that the molecular composition of Ef OM in the secondary effluent and reclaimed water was dominated by CHOS formulas, while NOM in the source water was dominated by CHO formulas. The CHO formulas of the three samples had similar origins. Anthropogenic surfactants were responsible for the CHOS formulas in Ef OM of the secondary effluent and were not well removed by the coagulation-sedimentation-ozonation treatment process adopted.     

Long-term effects of environmentally relevant concentrations of silver nanoparticles on microbial biomass, enzyme activity, and functional genes involved in the nitrogen cycle of loamy soil

The increasing production and use of engineered silver nanoparticles (AgNP) in industry and private households are leading to increased concentrations of AgNP in the environment. An ecological risk assessment of AgNP is needed, but it requires understanding the long term effects of environmentally relevant concentrations of AgNP on the soil microbiome. Hence, the aim of this study was to reveal the long-term effects of AgNP on soil microorganisms. The study was conducted as a laboratory incubation experiment over a period of one year using a loamy soil and AgNP concentrations ranging from 0.01 to 1?mg?AgNP/kg soil. The short term effects of AgNP were, in general, limited. However, after one year of exposure to 0.01?mg?AgNP/kg, there were significant negative effects on soil microbial biomass (quantified by extractable DNA; p?=?0.000) and bacterial ammonia oxidizers (quantified by amoA gene copy numbers; p?=?0.009). Furthermore, the tested AgNP concentrations significantly decreased the soil microbial biomass, the leucine aminopeptidase activity (quantified by substrate turnover; p?=?0.014), and the abundance of nitrogen fixing microorganisms (quantified by nifH gene copy numbers; p?=?0.001). The results of the positive control with AgNO3 revealed predominantly stronger effects due to Ag⁺ ion release. Thus, the increasing toxicity of AgNP during the test period may reflect the long-term release of Ag⁺ ions. Nevertheless, even very low concentrations of AgNP caused disadvantages for the microbial soil community, especially for nitrogen cycling, and our results confirmed the risks of releasing AgNP into the environment.     

Effects of chemical modification on physicochemical properties and adsorption behavior of sludge-based activated carbon

This study aimed to explore the adsorption performance of sludge-based activated carbon (SBC) towards dissolved organic matters (DOMs) removal from sewage, and investigated the modification effect of different types of chemicals on the structure of synthesized SBC. Waste activated sludge (WAS) was used as a carbon source, and HCl, HNO₃, and NaOH were used as different types of chemicals to modify the SBC. With the aid of chemical activation, the modified SBC showed higher adsorption performances on DOMs removal with maximum adsorption of 29.05 mg/g and second-order constant (k) of 0.1367 (L/mol/sec) due to the surface elution of ash and minerals by chemicals. The surface elemental composition of MSBC suggested that the content of C-C and C-O functional groups on the surface of modified sludge-based activated carbon (MSBC) played an important role on the adsorption capacities of MSBC towards DOMs removal in sewage. Additionally, the residual molecular weight of DOMs in sewage was investigated using a 3-dimension fluorescence excitation-emission matrix (3D-EEM) and high-performance size exclusion chromatography (HP-SEC). Results showed that the chemical modification significantly improved the adsorption capacity of MSBC on humic acids (HA) and aromatic proteins (APN), and both of NaOH-MSBC and HCl-MSBC were effective for a wide range of different AMW DOMs removal from sewage, while the HNO₃-MSBC exhibited poorly on AMW organics of 2,617 Da and 409 Da due to the reducing content of macropore. In brief, this study provides reference values for the impact of the chemicals of the activation stage before the SBCs application.     

水环境中溶解性有机物溯源分析及分子结构表征概述

溶解性有机物(DOM)是地球上最大的碳基化合物反应性储层之一,涉及各种生物地化反应并且在污染物溶解度、毒性、生物利用度、流变性和分布中发挥重要作用。本文介绍了当前用于表征水环境中DOM的策略和工具,探讨了当前研究在技术限制(预处理过程复杂、仪器分辨率低、数据处理困)、结构复杂性、结构多变性等方面存在的诸多局限性。分析认为:已有研究主要侧重于溯源分析和分子结构特征解析,未来研究应该在不同的结构层面和角度开展,加强多学科融合、数据库创建、对照实验和协同工作。