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.     

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.     

Effects of silver adsorbed on fumed silica, silver phosphate glass, bentonite organomodified with silver and titanium dioxide in aquatic indicator organisms

In order to reduce the level of transmission of diseases caused by bacteria and fungi, the development of antimicrobial additives for use in personal care, hygiene products, clothing and others has increased. Many of these additives are based on metals such as silver and titanium. The disposal of these products in the environment has raised concerns pertaining to their potential harmfulness for beneficial organisms. The objective of this study was to evaluate the influence of the shape, surface chemistry, size and carrier of three additives containing silver and one with titanium dioxide (TiO₂) on microcrustacean survival. Daphnia magna was used as a bioindicator for acute exposure test in suspensions from 0.0001 to 10,000 ppm. Ceriodaphnia dubia was used for chronic test in TiO₂ suspensions from 0.001 to 100 ppm. D. magna populations presented high susceptibility to all silver based additives, with 100% mortality after 24 hr of exposure. A different result was found in the acute experiments containing TiO₂ suspensions, with mortality rates only after 48 hr of incubation. Even on acute and chronic tests, TiO₂ did not reach a linear concentration-response versus mortality, with 1 ppm being more toxic than 10,000 ppm on acute test and 0.001 more toxic than 0.01 ppm on chronic assay. Silver based material toxicity was attributed to silver itself, and had no relation to either form (nano or ion) or carrier (silica, phosphate glass or bentonite). TiO₂ demonstrated to have a low acute toxicity against D. magna.     

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.     

Enhancement of elemental mercury adsorption by silver supported material

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO₂). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO₂ supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.     

Enhancement of elemental mercury adsorption by silver supported material

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO₂). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO₂ supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.     

两种粒径纳米银对Nitrosomonas europaea的毒性效应

为明晰不同粒径纳米银（AgNPs）对欧洲亚硝化毛杆菌（Nitrosomonas europaea）的毒性效应,采用室内培养方式,探究10nm和50nm的AgNPs对N.europaea生长、氮转化能力、细胞结构、活性氧生成和功能基因表达的影响.结果表明,AgNPs暴露抑制N.europaea生长,随着暴露时间的延长,细菌生长抑制率增加,在4h达到最大值;培养基中NH₄⁺向NO₂^-转化速率减缓,N.europaea的铵态氮转化能力降低;扫描电镜（SEM）图像显示AgNPs造成部分细菌表面塌陷且有孔洞,细胞膜受损严重;透射电镜（TEM）图像显示AgNPs造成细菌内部核物质消融,细胞质膜界限模糊;流式细胞仪（FCM）检测发现AgNPs增加细胞内活性氧的生成;qRT-PCR技术对AgNPs暴露后N.europaea功能基因amoA、hao、merA表达进行测定,发现AgNPs抑制N.europaea功能基因的转录表达.综上所述,AgNPs通过与细胞膜相互作用和产生氧化应激损伤N.europaea,抑制amoA和merA的表达,进而影响铵态氮转化过程,且小粒径AgNPs的毒性强于大粒径.     

江西赣州西坑银矿地质特征

西坑银矿为20世纪80年代在检查验证化探异常时发现的,后经详查评价确定为中低温热液充填交代形成的硅化破碎蚀变岩型银矿床,其银资源储量达中型规模。因其矿体硫化物少,蚀变弱,肉眼难于辨别,但银品位富等特点而倍受找矿界的关注。本文介绍了矿床的发现过程,成矿地质特征和找矿标志。     

Effect of natural organic matter on thallium and silver speciation

Natural organic matter (NOM) is known to play an important role in the transport and binding of trace metal elements in aquatic and soil systems. Thallium is a pollutant for which the extent of the role played by NOM is poorly known. Consequently, this study investigates thallium(I) and its complexation to a purified humic substance as proxy for NOM. Experiments were performed with the Donnan Membrane Technique to separate, for the first time, the free Tl⁺ ion from its complexed form in the bulk solution. Various pH and concentrations were investigated at constant ionic strength and constant NOM proxy concentrations in solution. Experimental results were described with NICA-Donnan model. Thallium complexation was compared to silver complexation using literature data and using the same NICA-Donnan formalism. Parameters for these two cations (Tl⁺ and Ag⁺) are reported in this article, for the first time. Results display low thallium complexation to the NOM proxy while silver competes with divalent cations for the NOM binding sites. Calculated speciation for dissolved thallium highlights the dominance of free thallium (Tl⁺) in solution whereas Tl-NOM complexes contribute roughly 15% to total Tl(I) species in river and lake type waters. Similar results are obtained for soil solutions, Tl-bound to NOM < 30% of total, from UK soils with different land use and geochemistry.     

从含银的废催化剂中回收白银

介绍了从含银的废催化剂中回收白银的一种新方法。采用氨浸A还原剂还原,浸出率98.5%,还原率99.9%,直接可获高纯度的银粉,金属银纯度可达99.9%。     

载银活性碳纤维对大肠杆菌吸附作用的研究

以大肠杆菌（Ｅｓｃｈｅｒｉｃｈｉａｃｏｌｉ）为对象，通过细菌吸附实验研究了载银活性碳纤维（ＡＣＦ（Ａｇ））对大肠杆菌的吸附特性．借助扫描电子显微镜（ＳＥＭ）进行细菌分布形态的观察和细菌数量的计算．结果表明，大肠杆菌易分布于ＡＣＦ（Ａｇ）表面的沟槽处；ＡＣＦ（Ａｇ）吸附的细菌数量随银含量、比表面积的增加而增大．此外，细菌吸附量还与ＡＣＦ（Ａｇ）表面银颗粒的大小有关．对吸附细菌的动力学亦进行了研究．     

纳米银与微塑料在模拟垃圾填埋柱中的共迁移特征

以模拟垃圾填埋柱和人工配制渗滤液,探讨了纳米银（AgNPs）和微塑料（MPs）在垃圾填埋场中的迁移行为.结果发现,无论是单体系还是二元体系,随着填埋时间增长,AgNPs和MPs颗粒在渗滤液中稳定性增强,在填埋场中迁移能力增大,可能导致填埋中晚期有更多的污染颗粒随渗滤液流出填埋场.当AgNPs和MPs共存时,相对于单体系促进了AgNPs的迁移而轻微地抑制了MPs的迁移.结合DLVO理论和胶体过滤理论分析,一方面是由于流动性更高的MPs可作为AgNPs的载体,同时与AgNPs竞争固相介质上的吸附位点,从而促进AgNPs的迁移.另一方面,共存的AgNPs降低了MPs颗粒的表面负电荷使其稳定性减弱,并通过预沉积在固相介质上提供额外的MPs沉积位点,从而抑制MPs的迁移.     

纳米银对小球藻光合作用和呼吸作用的影响

使用硼氢化钠还原硝酸银,聚乙烯醇(PVA)作为分散剂,制备出粒径为(7 ± 3)nm的纳米银,分别使用计数法和溶解氧法,研究了纳米银对小球藻(Chlorella vulgaris)生长、光合作用和呼吸作用的影响,并调查了对叶绿素a的抑制状况.结果显示,黑暗条件下加入3mg/L的纳米银,基本抑制了小球藻的呼吸作用,当暴露于4mg/L的纳米银时,小球藻生长的抑制率为93%;而光照条件下加入10mg/L纳米银时,才能抑制其光合作用,此时对小球藻生长的抑制率达到90%.光照时,叶绿素a在10mg/L纳米银的作用下,抑制率达到77%.研究表明了纳米银对小球藻呼吸作用有很强的抑制作用,对光合作用的影响可能通过抑制叶绿素a的合成或破坏叶绿体的结构来完成;光照能够明显减弱纳米银的毒性.     

Resistance and biosorption mechanism of silver ions by Bacillus cereus biomass

Biosorption of silver ions onto Bacillus cereus biomass was investigated. Overall kinetic experiments were performed for the determination of the necessary contact time for the attainment of equilibrium. It was found that the overall biosorption process was best described by pseudo second-order kinetic model. The crystals detected by scanning electron microscope and X-ray photoelectron spectroscopy suggested the precipitation was a possible mechanism of biosorption. The molecular genetics of silver resistance of B. cereus biomass was also detected and illustrated by a whole cell sensor tool.     

Environmental fate and behavior of silver nanoparticles in natural estuarine systems

Silver nanoparticles (AgNPs) are widely used in many consumer products, whereas their environmental behaviors in natural aquatic systems remain unknown, especially in natural brackish media. Therefore, it is urgent to investigate the environmental fate of AgNPs in natural brackish waters. Here, we investigated the stability of citrate-coated AgNPs in natural brackish water collected from 6 different sites with distinct salinities in the Xinglinwan Reservoir, located in Xiamen City, southeast China. The obtained results showed that AgNP colloids remained stable in low-salinity waters, which was mainly determined by the effects of dissolved organic matter (DOM) promoting the stability of the nanoparticles. However, the environmental fate of AgNPs in high-salinity waters was dominated by the salinity or ionic strength, especially the free ion concentrations of Cl^?, SO₄^2?, or S^2?, resulting in rapid sedimentation and dissolution. In addition, both DOM and salinity contributed to the environmental behavior of AgNPs in moderate-salinity waters, ultimately resulting in either colloidal stability or sedimentation. Overall, these results may reveal that AgNPs remain relatively stable for a long period in low-salinity natural waters, and that the stability might gradually decrease as AgNPs are transferred from freshwaters through brackish waters and eventually end up in seawater along the bay. Our findings also further indicate that the toxicity and potential risks of AgNPs may present more serious threats to the environment and organisms in natural freshwaters than in natural estuarine systems or seawater.     

银铜复合废料回收工艺研究

针对银铜复合废料回收的必要性，及国内外对银铜复合废料分离回收现状，实验研究了一套完整的银铜分离回收工艺，该工艺具有高效、简便、低成本、少污染等优点，铜回收率达99．7％，银回收率大于99．9％，回收铜、银的纯度高于99．9％。