Is there a silver lining? Aggregation and photo-transformation of silver nanoparticles in environmental waters

Is the aggregation of silver nanoparticles in environmental waters a silver lining? The answer is not simple. Clearly, however, the aggregation and photo-transformation of AgNPs are complicated and could be more significant than previously thought. The difference in the water chemistry that controls the aggregation and photo-transformation of AgNPs results in the varying behavior and fate of AgNPs among different water bodies.     

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.     

Characterisation of dissolved organic matter in stormwater using high-performance size exclusion chromatography

Understanding the complexity of dissolved organic matter(DOM)in stormwater has drawn a lot of interest,since DOM from stormwater causes not only environmental impacts,but also worsens downstream aquatic quality associated with water supply and treatability.This study introduced and employed high-performance size exclusion chromatography(HPSEC)coupled with an ultraviolet–visible(UV–vis)diode array detector to assess changes in stormwater-associated DOM characteristics.Stormwater DOM was also analysed in relation to storm event characteristics,water quality and spectroscopic analysis.Statistical tools were used to determine the correlations within DOM and water quality measurements.Results showed that dissolved organic carbon(DOC)and UV absorbance at 254 nm(UV_(254))as conventional DOM parameters were found to be correlated well to the changes in stormwater quality during each of the three storm events studied.Both detector wavelengths(210and 254 nm)and their ratio(A_(210)/A_(254))were found to provide additional information on the physiochemical properties of stormwater-associated DOM.This study indicated that A_(210)/A_(254) is an important parameter which could be used to estimate the DOM proportions of functional groups and conjugated carbon species.This study provided also an understanding of stormwater quality constituents through assessing variability and sensitivity for various parameters,and the additional information of rainfall characteristics on runoff quality data for a better understanding of parameter correlations and influences.     

纳米银在环境水样和实验介质中的理化性质和毒性效应

纳米银在自然环境中的理化性质可能严重影响其环境效应,本文的目的是为了比较纳米银在自然水样和实验介质条件下的理化性质和毒性效应.实验表征了粒径4 nm表面包裹物为油胺的纳米银,在不同介质条件下的粒径和团聚性,并进一步研究了不同环境介质条件下纳米银暴露对枯草芽孢杆菌的毒性效应.透射电镜照片显示油胺包裹的4 nm纳米银在环境介质中发生明显团聚.油胺包裹的4 nm纳米银暴露会抑制培养基中细菌的生长速率,降低生理盐水溶液中细菌的存活率.纳米银在实验条件下对细菌的毒性呈一定剂量效应关系,但是在环境水样中剂量效应关系不明显.低浓度纳米银在环境水样中的毒性比其在实验介质中弱.纳米银的透析袋暴露实验中,细菌的存活率有显著提升,揭示纳米银与细菌的直接相互作用对毒性效应有重要作用.与实验条件的培养基和生理盐水介质相比,环境水样中的纳米银更趋向以团聚形式存在,与细菌的相互作用几率减小,因此纳米银在环境介质中对细菌的毒性会降低.     

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.     

Photocatalytic reduction of organic pollutant under visible light by green route synthesized gold nanoparticles

We report a rapid method of green chemistry approach for synthesis of gold nanoparticles(AuNPs)using Lagerstroemia speciosa leaf extract(LSE). L. speciosa plant extract is known for its effective treatment of diabetes and kidney related problems. The green synthesis of Au NPs was complete within 30 min at 25°C. The same could also be achieved within 2 min at a higher reaction temperature(80°C). Both UV–visible spectroscopy and transmission electron microscopy results suggest that the morphology and size distribution of Au NPs are dependent on the pH of gold solution,gold concentration,volume of LSE,and reaction time and temperature. Comparison between Fourier transform infrared spectroscopy(FT-IR)spectra of LSE and the synthesized Au NPs indicate an active role of polyphenolic functional groups(from gallotannins,lagerstroemin,and corosolic acid)in the green synthesis and capping of Au NPs. The green route synthesized Au NPs show strong photocatalytic activity in the reduction of dyes viz.,methylene blue,methyl orange,bromophenol blue and bromocresol green,and 4-nitrophenol under visible light in the presence of Na BH_4. The non-toxic and cost effective LSE mediated Au NPs synthesis proposed in this study is extremely rapid compared to the other reported methods that require hours to days for complete synthesis of Au NPs using various plant extracts. Strong and stable photocatalytic behavior makes Au NPs attractive in environmental applications,particularly in the reduction of organic pollutants in wastewater.     

人工纳米颗粒对水生生物的毒性效应及其机制研究进展

随着纳米科技的飞速发展和纳米产品的普及,人工纳米颗粒(NPs)的生物毒性效应研究逐渐成为国内外关注的热点.以水环境和水生生物为对象,综述了近几年来NPs对水生生物的毒性效应、毒性机制等方面的研究进展.文中按NPs的分类总结了NPs对微生物、藻类、原生动物和鱼类等水生生物的毒性效应,着重论述了NPs的可能毒性机制及其与NPs的独特物理化学性质之间的关系,并在细胞和分子水平上探讨了NPs的摄取、跨膜运输等方面的可能机制.在自然水体中,NPs因其化学行为受水化学条件等影响而表现出不同于实验室研究中的生物毒性效应,本文也对这方面的研究进行了讨论和总结.最后分析了目前水生生物纳米毒性研究中的瓶颈和方法、技术方面的问题,并对以后应注重开展的研究进行了展望.     

三峡库区典型农业小流域水体中溶解性有机质的光谱特征

溶解性有机质(DOM)作为重要的地球化学因子,在流域水体环境中扮演着重要的作用.本研究以三峡库区消落带典型农业小流域——重庆涪陵区王家沟为研究对象,结合该流域内不同土地利用类型,通过紫外-可见光吸收和荧光光谱,对小流域内水体DOM的光谱特征进行了表征和分析.结果表明,该农业小流域水体DOM空间差异较大,其组成和来源均存在明显不同.CDOM在DOM中所占比例[a*_g(355)]大小顺序为:稻田水沟渠水池塘水井水出口水,其中稻田水和沟渠水的SUVA_(254)较井水和出口水大,芳香性更明显.三维荧光光谱中2类4个荧光峰(A、C和B、T),DOM来源都是内部(微生物、藻类)以及外源(腐殖质)的双重贡献.除自生源微生物活动的影响外,外源生活污水和农业生产用水的影响也是导致DOM组分中类蛋白组分增多的重要原因.对比了不同种植季时相同位置水样DOM光谱特征,类蛋白组分是控制两个种植季水体DOM特征波动的重要因素.土地使用方式变化后水体DOC、CDOM和DOM当中的类蛋白/类腐殖荧光组分[r_(T/C)]比例存在明显差异,而FI、BIX和r_(A/C)差异不显著.     

Synthesis,crystal structure,photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c = 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^− 1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2 − and NO₃⁻, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography–mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.     

Photodegradation of methylmercury in Jialing River of Chongqing,China

Photodegradation (PD) of methylmercury (MMHg) is a key process of mercury (Hg) cycling in water systems, maintaining MMHg at a low level in water systems. However, we possess little knowledge of this important process in the Jialing River of Chongqing, China. In situ incubation experiments were thus performed to measure temporal patterns and influencing factors of MMHg PD in this river. The results showed that MMHg underwent a net demethylation process under solar radiation in the water column, which predominantly occurred in surface waters. For surface water, the highest PD rate constants were observed in spring (12 × 10^− 3 ± 1.5 × 10^− 3 m²/E), followed by summer (9.0 × 10^− 3 ± 1.2 × 10^− 3 m²/E), autumn (1.4 × 10^− 3 ± 0.12 × 10^− 3 m²/E), and winter (0.78 × 10^− 3 ± 0.11 × 10^− 3 m²/E). UV-A radiation (320–400 nm), UV-B radiation (280–320 nm), and photosynthetically active radiation (PAR, 400–700 nm) accounted for 43%–64%, 14%–31%, and 16%–45% of MMHg PD, respectively. PD rate constants varied substantially with the treatments that filtered the river water and amended it with chemicals (i.e., Cl⁻, NO₃⁻, dissolved organic matter (DOM), Fe(III)), which reveals that suspended particulate matter and water components are important factors in affecting the PD process. For the entire water column, the PD rate constant determined for each wavelength range decreased rapidly with water depth. UV-A, UV-B, and PAR contributed 27%–46%, 6.2%–12%, and 42%–65% to the PD process, respectively. PD flux was estimated to be 4.7 μg/(m²·year) in the study site. Our results are very important to understand the cycling characteristics of MMHg in the Jialing River of Chongqing, China.     

典型工程纳米材料对微藻的毒性效应研究进展

近年来,随着纳米技术的快速发展,工程纳米材料由于其良好的物理化学特性而广泛应用于各行各业。然而,在生产、使用和丢弃含有工程纳米材料产品的过程中不可避免地导致纳米材料释放到水环境中。工程纳米材料已在世界多地的水环境中被检测到,给水生态系统和人体健康带来潜在风险。由于水环境的复杂性,工程纳米材料在水体中的环境行为、毒性效应等生态风险还未得到充分的研究。本文以微藻为模型生物,总结了典型工程纳米材料,包括纳米金属、纳米氧化物、碳纳米材料以及量子点的毒性效应。探讨了工程纳米材料在水中的环境行为以及与其它污染物的复合毒性效应,讨论了工程纳米材料自身理化性质和环境因素对其毒性的影响。从生理指标和组学指标出发分析了工程纳米材料对微藻的毒性机制,并展望了工程纳米材料毒性研究的发展方向,以期为工程纳米材料的毒性评价提供一定的理论依据,促进纳米材料的绿色发展。     

High-performance size exclusion chromatography with a multi-wavelength absorbance detector study on dissolved organic matter characterisation along a water distribution system

This study examined the associations between dissolved organic matter(DOM) characteristics and potential nitrification occurrence in the presence of chloramine along a drinking water distribution system. High-performance size exclusion chromatography(HPSEC) coupled with a multiple wavelength detector(200–280 nm) was employed to characterise DOM by molecular weight distribution, bacterial activity was analysed using flow cytometry, and a package of simple analytical tools, such as dissolved organic carbon, absorbance at 254 nm, nitrate,nitrite, ammonia and total disinfectant residual were also applied and their applicability to indicate water quality changes in distribution systems were also evaluated. Results showed that multi-wavelength HPSEC analysis was useful to provide information about DOM character while changes in molecule weight profiles at wavelengths less than 230 nm were also able to be related to other water quality parameters. Correct selection of the UV wavelengths can be an important factor for providing appropriate indicators associated with different DOM compositions. DOM molecular weight in the range of 0.2–0.5 k Da measured at210 nm correlated positively with oxidised nitrogen concentration(r = 0.99), and the concentrations of active bacterial cells in the distribution system(r = 0.85). Our study also showed that the changes of DOM character and bacterial cells were significant in those sampling points that had decreases in total disinfectant residual. HPSEC-UV measured at210 nm and flow cytometry can detect the changes of low molecular weight of DOM and bacterial levels, respectively, when nitrification occurred within the chloraminated distribution system.     

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.     

辽河流域河流秋季CDOM光学特性及影响因素研究

了解有色溶解有机物(CDOM)的光学特性有助于对水生生态系统中溶解有机物(DOM)循环过程的研究,而环境要素对CDOM光学特性的影响会进一步影响水环境中的碳循环过程.利用2013年9月和10月辽河水体实测数据对水体反射特性、CDOM的吸收特性、荧光特性及各种水质参数对CDOM光学特性的影响进行研究.结果表明,辽河流域河流总氮(均值4.40 mg·L~(-1))、铬浓度(均值0.0065 mg·L~(-1))超过国家地表水V类标准.悬浮泥沙光谱特征较为明显的水样,其CDOM的吸收曲线非常相近,叶绿素a光谱特征较为明显的水样,其CDOM吸收曲线之间的差别较大.辽河流域水体CDOM的吸收斜率S275-295(0.0163~0.0191 nm-1)高于其他大多数河流,而低于湖泊、水库.对比辽河流域河流发现,东辽河与辽河水体CDOM组成物质的分子量相对较小,东辽河CDOM的芳香性最高,而西辽河最低.根据荧光指数、腐殖化指数及生物源指数分析发现,辽河流域水体主要以陆源的、高等植物DOM为主,太子河、大凌河CDOM具有较为明显的自生源特征.通过荧光峰的分布发现,辽河水体CDOM以类腐殖酸荧光峰(A峰、C峰)为主,部分河流(辽河干流)同时表现出较强的类蛋白质荧光峰(B峰、T峰).通过冗余分析(RDA)发现,水体中溶解有机碳(DOC)、总氮(TN)、总磷(TP)、总碱度(TAlk)、砷(As)及汞(Hg)与表征CDOM光学特性的参数之间存在显著的相关性(p0.05),是CDOM光学特征的主要影响因子.     

Synthesis, characterization, and photocatalytic activity of porous La–N–co-doped TiO2 nanotubes for gaseous chlorobenzene oxidation

The photocatalytic oxidation of gaseous chlorobenzene(CB) by the 365 nm-induced photocatalyst La/N–Ti O2, synthesized via a sol–gel and hydrothermal method, was evaluated. Response surface methodology(RSM) was used to model and optimize the conditions for synthesis of the photocatalyst. The optimal photocatalyst was 1.2La/0.5N–Ti O2(0.5) and the effects of La/N on crystalline structure, particle morphology, surface element content, and other structural characteristics were investigated by XRD(X-ray diffraction), TEM(Transmission Electron Microscopy), FTIR(Fourier transform infrared spectroscopy), UV–vis(Ultraviolet–visible spectroscopy), and BET(Brunauer Emmett Teller). Greater surface area and smaller particle size were produced with the co-doped Ti O2 nanotubes than with reference Ti O2. The removal of CB was effective when performed using the synthesized photocatalyst,though it was less efficient at higher initial CB concentrations. Various modified Langmuir-Hinshelwood kinetic models involving the adsorption of chlorobenzene and water on different active sites were evaluated. Fitting results suggested that competitive adsorption caused by water molecules could not be neglected, especially for environments with high relative humidity. The reaction intermediates found after GC–MS(Gas chromatography–mass spectrometry) analysis indicated that most were soluble, low-toxicity, or both. The results demonstrated that the prepared photocatalyst had high activity for VOC(volatile organic compounds) conversion and may be used as a pretreatment prior to biopurification.     

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.     

夏、冬季降雨中溶解性有机质(DOM)光谱特征及来源辨析

利用紫外-可见光谱与三维荧光光谱,结合拉格朗日混合单粒子轨道模型及火点图,研究了重庆2013年夏、冬两季雨水DOM光谱特征,并对其来源进行解析.结果表明,雨水DOM与水体、土壤DOM具有类似性质光谱特征,证明降雨DOM也是陆地及水环境中DOM地化特征的重要贡献者.雨水DOM中DOC含量为0.88~12.80 mg·L-1,CDOM含量在3.17~21.11m-1之间,夏、冬两季降雨DOM差异明显(P0.05).与夏季相比,冬季降雨DOM分子量较小,芳香性程度较低,腐殖化程度也更低,输入主要以本地和短距离输送为主;而夏季DOM来源较分散.尽管吸收和荧光光谱可用于解析雨水DOM组成和来源,但在光谱特征的解析和来源识别上与其他来源DOM有所区别,传统"内、外源区分"并不适用于雨水DOM.     

Effects of ionic strength and temperature on the aggregation and deposition of multi-walled carbon nanotubes

The aggregation and deposition of carbon nanotubes(CNTs) determines their transport and fate in natural waters.Therefore,the aggregation kinetics of humic-acid treated multi-walled carbon nanotubes(HA-MWCNTs) was investigated by time-resolved dynamic light scattering in NaCl and CaCl_2 electrolyte solutions.Increased ionic strength induced HA-MWCNT aggregation due to the less negative zeta potential and the reduced electrostatic repulsion.The critical coagulation concentration(CCC) values of HA-MWCNTs were 80 mmol/L in NaCl and 1.3 mmol/L in CaCl_2 electrolyte,showing that Ca~(2+) causes more serious aggregation than Na~+.The aggregation behavior of HA-MWCNTs was consistent with Derjaguin-Landau-Verwey-Overbeek theory.The deposition kinetics of HA-MWCNTs was measured by the optical absorbance at 800 ran.The critical deposition concentrations for HA-MWCNT in NaCl and CaCl_2 solutions were close to the CCC values,therefore the rate of deposition cannot be increased by changing the ionic strength in the diffusion-limited aggregation regime.The deposition process was correlated to the aggregation since larger aggregates increased gravitational deposition and decreased random Brownian diffusion.HA-MWCNTs hydrodynamic diameters were evaluated at 5,15 and 25℃.Higher temperature caused faster aggregation due to the reduced electrostatic repulsion and increased random Brownian motion and collision frequency.HA-MWCNTs aggregate faster at higher temperature in either NaCl or CaCl_2electrolyte due to the decreased electrostatic repulsion and increased random Brownian motion.Our results suggest that CNT aggregation and deposition are two correlated processes governed by the electrolyte,and CNT transport is favored at low ionic strength and low temperature.     

Comparison of surface water chemistry and weathering effects of two lake basins in the Changtang Nature Reserve, China

The geochemistry of natural waters in the Changtang Nature Reserve,northern Tibet,can help us understand the geology of catchments,and provide additional insight in surface processes that influence water chemistry such as rock weathering on the Qinghai–Tibet Plateau.However,severe natural conditions are responsible for a lack of scientific data for this area.This study represents the first investigation of the chemical composition of surface waters and weathering effects in two lake basins in the reserve(Lake Dogaicoring Qiangco and Lake Longwei Co).The results indicate that total dissolved solids(TDS)in the two lakes are significantly higher than in other gauged lakes on the Qinghai–Tibet Plateau,reaching 20–40 g/L,and that TDS of the tectonic lake(Lake Dogaicoring Qiangco)is significantly higher than that of the barrier lake(Lake Longwei Co).Na+and Cl-are the dominant ions in the lake waters as well as in the glacier-fed lake inflows,with chemical compositions mainly affected by halite weathering.In contrast,ion contents of inflowing rivers fed by nearby runoff are lower and concentrations of dominant ions are not significant.Evaporite,silicate,and carbonate weathering has relatively equal effects on these rivers.Due to their limited scope,small streams near the lakes are less affected by carbonate than by silicate weathering.