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.     

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.     

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.     

海水入侵区含水层中原核微生物多样性和群落结构特征及其意义

海水入侵引起的地下水咸化是沿海地区面临的主要自然灾害之一,并由此产生了强烈的物理化学梯度变化,严重影响了原生态环境. 为研究海水入侵影响下含水层微生物的多样性和群落结构,揭示海水入侵对原位微生物群落的环境影响,采用基于高通量测序的微生物群落分析方法,对珠江三角洲含水层中微生物群落多样性和结构组成进行表征和比较,并探讨微生物群落对环境变化的响应. 结果表明:研究区地下水中微生物群落主要分属于47个原核微生物门类,其中最丰富的门是变形菌门(Proteobacteria),其次是厚壁菌门(Firmicutes)、放线菌门(Actinobacteria)和拟杆菌门(Bacteroidetes),而古菌的群落结构以奇古菌(Thaumarchaeota)和广古菌(Euryarchaeota)为主,且Thaumarchaeota和Euryarchaeota在高浓度咸水中丰富度更高. 不同盐度梯度下微生物群落之间共有的OTUs占比为59%,在一些高浓度咸水样品中存在大量的脱硫弧菌属和甲烷球菌厌氧微生物. 虽然微生物群落的多样性并不完全与盐度梯度一致,但在溶解性总固体(TDS)浓度大于1 g/L的含盐地下水中,微生物群落的多样性随盐度的增加而增加. 典范对应分析(CCA)表明,TDS和总氮(TN)是影响微生物群落分布最显著的环境因子. 研究结果为进一步揭示海水侵蚀下的地下水中微生物群落的结构及其环境相互作用奠定了基础.      

辽河流域与英国中部河湖水体中溶解有机质的荧光特性

运用三维荧光光谱技术对辽河流域和英国中部水体中溶解有机质(DOM)的荧光光谱特性进行了分析.结果表明,辽河流域各研究水体中DOM包含4种荧光组分,即类色氨酸、类酪氨酸、可见光区和紫外光区类腐殖质,通过对荧光特性定量指标的分析可知,辽河流域各研究断面水体中类腐殖质物质内源作用大于陆源,DOM具有较强的新近自生源,各河流水体中DOM腐殖化程度顺序为:浑河中游海城河中游蒲河下游太子河下游.相比之下,英国河湖中,除了River Tame含有以上4种荧光组分外,其它水体中均没有发现类酪氨酸荧光物质,甚至在River Tern中仅含有类腐殖质荧光物质,河湖中DOM含有较少的新近自生源组分,以陆源影响为主.另外,辽河流域水体中类蛋白与类腐殖质荧光峰强度比值大于英国各河流水体的平均值.由此可以推断,辽河流域各研究断面大量污染物的输入,是造成其严重内源污染的主要原因,从而使水体中DOM含量增加,英国各河流断面其DOM主要来自于水体本身存在的大量微生物和浮游植物的代谢活动以及土壤有机质经雨水的冲刷流入水体的贡献.     

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.     

氧化石墨烯在不同盐度水体中的聚沉行为研究

研究氧化石墨烯（GO）的水环境行为对于阐明其生态风险具有重要意义。本文将GO分散于不同盐度的水体中,研究了GO在水环境中的分散稳定性及聚沉行为。结果表明,GO能够均匀分散于去离子水中,且降低溶液的pH。随着静置时间的延长,GO产生缓慢聚沉。随分散水体盐度增加,GO溶液的聚沉速率快速增加,聚沉颗粒粒径明显增加;当水体盐度达到8~10后,GO溶液的聚沉速率趋于理想状态下的快速聚沉速率。GO在不同盐度海水中的聚沉服从经典的胶体稳定性理论,其聚集效率随盐度的增加呈现两阶段过程。由此计算出2~100 mg/L的GO溶液的临界团聚盐度为6.79~11.84。由此可见,较稳定分散于淡水水体的GO可能对淡水生物产生较高的生态风险,而在海水中易于聚沉的GO可能对近海底栖生物存在较高的生态风险。     

Understanding the risks of mercury sulfide nanoparticles in the environment: Formation, presence, and environmental behaviors

Mercury (Hg) could be microbially methylated to the bioaccumulative neurotoxin methylmercury (MeHg), raising health concerns. Understanding the methylation of various Hg species is thus critical in predicting the MeHg risk. Among the known Hg species, mercury sulfide (HgS) is the largest Hg reservoir in the lithosphere and has long been considered to be highly inert. However, with advances in the analytical methods of nanoparticles, HgS nanoparticles (HgS NPs) have recently been detected in various environmental matrices or organisms. Furthermore, pioneering laboratory studies have reported the high bioavailability of HgS NPs. The formation, presence, and transformation (e.g., methylation) of HgS NPs are intricately related to several environmental factors, especially dissolved organic matter (DOM). The complexity of the behavior of HgS NPs and the heterogeneity of DOM prevent us from comprehensively understanding and predicting the risk of HgS NPs. To reveal the role of HgS NPs in Hg biogeochemical cycling, research needs should focus on the following aspects: the formation pathways, the presence, and the environmental behaviors of HgS NPs impacted by the dominant influential factor of DOM. We thus summarized the latest progress in these aspects and proposed future research priorities, e.g., developing the detection techniques of HgS NPs and probing HgS NPs in various matrices, further exploring the interactions between DOM and HgS NPs. Besides, as most of the previous studies were conducted in laboratories, our current knowledge should be further refreshed through field observations, which would help to gain better insights into predicting the Hg risks in natural environment.     

Salinity discrimination in harbour seals: a sensory basis for spatial orientation in the marine environment?

 Salinity variations can be considered as a potential source of information for orientation in the marine environment. To use this kind of environmental information marine animals must be able to detect these salinity differences. Therefore we determined salinity-difference thresholds of two harbour seals for the discrimination of seawater solutions as a function of the salinity level (15–35‰) and compared them with the thresholds of human subjects. Whereas in humans thresholds increased with increasing salinity level, thresholds of seals decreased with increasing salinity level. Both seals achieved best sensitivity at 30‰ salinity, where they detected a salinity difference ≤4%. These data indicate that the ability of seals to detect salinity differences of seawater is well tuned to the natural occurrence of this environmental information. Their high gustatory resolving power for differences in seawater salinity is suggested to meet the basic requirements for chemosensory orientation of seals in the marine habitat. Received: 10 February 2000 / Accepted in revised form: 19 September 2000     

How do water striders, Aquarius paludum, react to brackish water simulated by NaCl solutions?

Several stages, from eggs to adults, of the water strider, Aquarius paludum (Fabricius), inhabiting fresh water are sometimes conveyed by heavy flow in the rainy or typhoon seasons in Japan to lotic brackish water in the mouth of rivers. The water striders might then respond to salinity either by remaining to wait for extensive rainfall to reduce osmotic pressure locally before reproducing (“breed here and later tactic”) or by flying away to reproduce in fresh waters elsewhere (“breed elsewhere and later tactic”). All first instars died before the first molt when they were exposed to 1.75 and 3.5% NaCl solutions in a laboratory experiment. Living on 0.5 and 0.9% solutions through larval and adult stages slowed down larval growth and suppressed female reproduction. When exposed to the 0.5 and 0.9% solutions, 90 and 92% of males, respectively, showed histolysis of their flight muscles. Therefore, in brackish natural habitats, larvae and adults seem to follow the strategy “breed here and later.” When water striders were exposed to 0.9% solution either just after emergence or 20 days later, females showed a higher flight propensity than those kept on fresh waters throughout, and they delayed the deposition of eggs. Therefore, when conveyed to brackish water after emergence by stream flow after heavy rain, adults seem to leave the area by flight, demonstrating the strategy “breed elsewhere and later” tactic. We conclude that water striders use alternative tactics for responding to salinity, depending on the stage of exposure.     

泥沙沉降对水体中溶解性有机物光谱学特性的影响

以沈阳市新开河为研究对象,考察了泥沙沉降过程中,沉降时间、泥沙含量、pH、盐度对水体中溶解性有机物(DOM)的含量和光谱学特性的影响.结果表明,泥沙沉降条件下,水体中DOC随泥沙沉降时间的增长而先增大后减小,随泥沙含量的增加而先减小后增大,随pH的增大而增大,随盐度的增大而减小.随着pH的增大,水体中DOM的芳香性增强;随着盐度的增大,水体中DOM的芳香性降低.随着泥沙沉降时间的增长,DOM中各类荧光物质的含量先增加后减少;随着泥沙含量的增加,DOM中类腐殖酸和类富里酸荧光物质的含量增加,而类溶解性微生物代谢产物荧光物质和类芳香族蛋白质荧光物质的含量降低.在泥沙沉降过程中,下层水体中DOC、在波长为254 nm处的紫外吸光度(UV-254),以及DOM中荧光物质含量的变化量高于上层水体.     

Biochar affects methylmercury production and bioaccumulation in paddy soils: Insights from soil-derived dissolved organic matter

Biochar has been used increasingly as a soil additive to control mercury (Hg) pollution in paddy rice fields. As the most active component of soil organic matter, soil dissolved organic matter (DOM) plays a vital role in the environmental fate of contaminants. However, there are very few studies to determine the impact of biochar on the Hg cycle in rice paddies using insights from DOM. This study used original and modified biochar to investigate their effect on DOM dynamics and their potential impact on methylmercury (MeHg) production and bioaccumulation in rice plants. Porewater DOM was collected to analyze the variations in soil-derived DOM in paddy soils. The results showed that the addition of biochar, whether in original or modified form, significantly reduced the bioaccumulation of MeHg in rice plants, especially in hulls and grains (p<0.05). However, MeHg production in soils was only inhibited by the modified biochar. Biochar addition induced a significant increase in DOM's aromaticity and molecular weight (p<0.05), which decreased Hg bioavailability. Furthermore, enhanced microbial activity was also observed in DOM (p<0.05), further increasing MeHg production in the soil. Thus, the effect of biochar on the fate of Hg cycle involves competition between the two different roles of DOM. This study identified a specific mechanism by which biochar affects Hg behavior in rice paddy soil and contributes to understanding the more general influence of biochar in agriculture and contaminant remediation.     

长期不同水分调控对污染场地土壤溶解性有机质含量及其结构特征的影响

为了考察不同水分调控下污染场地中土壤有机质和溶解性有机质（DOM）的演变过程,以2种冶炼厂重金属污染土壤为研究对象,通过恒温恒湿培养实验观察不同水分调控下土壤有机质和DOM的含量变化,并采用紫外-可见光谱和荧光光谱分析了土壤DOM的光谱特征.结果表明,水分调控180 d后,2种重金属污染土壤中有机质和DOM含量呈不同程度降低趋势,且随着水分含量增加,其降幅明显增加,最大降幅分别为33.28%和89.35%.水分调控过程中,土壤DOM中类蛋白物质最易发生降解,导致类富里酸和类腐殖酸的占比相应提高;随着水分含量增加,土壤DOM的芳香性提高,腐殖化程度升高,分子聚合度和分子量增大,最终导致DOM稳定性增强,上述结果有助于揭示水分诱导过程中DOM的变化对污染场地中重金属环境行为的影响.     

45#钢和Q235在不同水环境中的腐蚀行为研究

目的研究碳钢在不同水环境条件下的腐蚀行为。方法通过开展45#钢及Q235两种典型的碳钢材料在淡海水交替、海水及淡水自然环境下2年的暴露试验,将三种环境下材料的腐蚀形貌、腐蚀速率进行对比,总结3种材料在不同水环境下的腐蚀规律,对其腐蚀机理进行了简要的探讨,并对其长周期的腐蚀行为进行预测。结果对45#钢来说,淡海水环境对其的影响是海水环境下的92%,淡水环境的影响是海水环境下的46%;对Q235来说,淡海水环境对其的影响是海水环境下的88%,淡水环境的影响是海水环境的53%。结论碳钢在海水环境下耐蚀性最差,在淡海水交替自然环境下次之,在淡水环境下的耐蚀性能最好。     

渤海湾两条河流及其近岸海域水体中DOM的光谱特征及影响因素

应用三维荧光光谱结合吸收光谱分析,研究了2019年夏季天津市大清河-独流减河水系和河北省黄骅市捷地减河及其河口区水体中溶解有机物（DOM）的空间分布特征、来源及其影响因素。紫外-可见光谱结果表明,研究区水体的SUVA₂₅₄与盐度有显著正相关关系;两条河流的下游水体中S_275-295均值均大于上游和中游。平行因子分析结果表明,两条河流均检测到两种类腐殖质组分C1（240,300/390 nm）和C3（260,335/477 nm）以及一种类蛋白质组分C2（225,275/339 nm）。在大清河-独流减河水系及其近岸海域水体中,这三种组分与盐度呈显著负相关关系,其中由于人为输入（TN和TP含量高,工业排污）影响导致C2与盐度的相关性弱于C1和C3。该水系水体在低盐度时C2的占比高于捷地减河,主要受到工农业废水输入与其支流子牙河汇入的共同影响,而捷地减河主要受农业废污水输入的影响。此外,自然因素（盐度、海水混合）和人为因素（人为输入、筑坝拦截）的不同导致渤海湾两条入海河流中有色溶解有机质（CDOM）的光学特性和混合行为出现显著差异。其中筑坝拦截导致独流减河坝前水体的CDOM平均分子量低于下游水体,并且增强了河口区陆源类腐殖质的去除作用。综上,三维荧光光谱结合平行因子分析能判别河流局部条件的差异对整体CDOM空间分布特征的影响,研究结果可为渤海湾地区河流及河口水体CDOM生物地球化学过程研究提供基础数据。     

DAX-8和XAD-4串联树脂法大体积提取海水溶解有机质及其分子组成分析

采用DAX-8和XAD-4串联树脂技术（DAX-8/XAD-4法）对青岛近海表层海水的溶解有机质（dissolved organic matter,DOM）进行了大体积的提取制备,获得DOM中的疏水酸性组分（hydrophobic acid,HOA）、亲水酸性组分（hydrophilic acid,HIA）、疏水中性组分（hydrophobic neutral,HON）和亲水中性组分（hydrophilic neutral,HIN）共4个组分。从200 L海水中共提取海洋DOM固体样品0.3 g,总有机碳提取效率为48%。应用傅立叶变换离子回旋共振质谱（Fourier transform ion cyclotron resonance mass spectrometry, FT-ICR MS）对得到的4个组分进行分子组成表征。结果表明,酸性组分（HOA和HIA）可鉴别出4000余个分子,具有相对较高的O/C值,其氧化降解程度较高;中性组分鉴别出1000余个分子,其H/C值较高,具有较低的缩合度。含氮类化合物在亲水组分（HIA和HIN）中相对富集。富羧基脂环化合物（carboxylic-rich alicyclic molecules,CRAM）在酸性组分中相对富集。DAX-8/XAD-4树脂串联法能用于含盐高、DOM含量低的海水,适用于分离提取大体积海水样品中不同极性的DOM亚组分,其样品量及较低的灰分能满足分析表征和模拟实验等应用需求。     

淹水条件下三峡库区典型消落带土壤释放DOM的光谱特征:荧光光谱

作为水体DOM的重要来源,消落带土壤淹水释放过程十分重要.本文以三峡库区典型消落带土壤为例,通过模拟正常淹水和厌氧淹水的两种条件,利用荧光光谱,着重定性地分析并讨论了土壤向上覆水体释放DOM的动态特征.结果表明,消落带4个区域土壤淹水后产生的DOM荧光特性,呈现出和可见-紫外光谱相似特征,对上覆水体DOM荧光特征有重要贡献.淹水初期的快速释放及后期去除机制,是水体DOM荧光组分的动态"源-汇"平衡的关键;其中类腐殖峰(A和C)受无机矿物相的吸附-释放影响明显,而类蛋白峰(B和T)受微生物影响较为明显.另外,所有土壤淹水释放后水体DOM均呈现出"内源+外源"的复合特征.除忠县石宝寨(SB)外,整个淹水周期,其余区域土壤在厌氧和正常淹水条件下,水体DOM荧光特征的差异性不明显,这可能和土壤自身组成(例如无机矿物组成和有机组分)的复杂程度有关.结合可见-紫外光谱,两种技术相互补充,证明了土壤释放("源")和去除("汇")机制是控制DOM动态变化的重要因素;而淹水初期的较强芳香性和腐殖化程度,以及较强的陆源特征,无疑有利于进一步解释污染物在淹水过程中的环境行为,为进一步了解DOM的环境角色提供数据基础和实验支撑.