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.     

Influences of anion concentration and valence on dispersion and aggregation of titanium dioxide nanoparticles in aqueous solutions

Dispersion and aggregation of nanoparticles in aqueous solutions are important factors for safe application of nanoparticles. In this study, dispersion and aggregation of nano-TiO₂ in aqueous solutions containing various anions were investigated. The influences of anion concentration and valence on the aggregation size, zeta potential and aggregation kinetics were individually investigated. Results showed that the zeta potential decreased from 19.8 to − 41.4 mV when PO₄^3 − concentration was increased from 0 to 50 mg/L, while the corresponding average size of nano-TiO₂ particles decreased from 613.2 to 540.3 nm. Both SO₄^2 − and NO₃⁻ enhanced aggregation of nano-TiO₂ in solution. As SO₄^2 − concentration was increased from 0 to 500 mg/L, the zeta potential decreased from 19.8 to 1.4 mV, and aggregate sizes increased from 613.2 to 961.3 nm. The trend for NO₃⁻ fluctuation was similar to that for SO₄^2 − although the range of variation for NO₃⁻ was relatively narrow. SO₄^2 − and NO₃⁻ accelerated the aggregation rapidly, while PO₄^3 − did so slowly. These findings facilitate the understanding of aggregation and dispersion mechanisms of nano-TiO₂ in aqueous solutions in the presence of anions of interest.     

天然水体中多壁纳米碳管对纳米氧化锌颗粒团聚与沉降行为的影响

研究了淡水湖泊水体中氧化多壁纳米碳管(Oxidized-multiwalled carbon nanotubes,o-MWCNTs)对纳米氧化锌(ZnO nanoparticles,nZnO)颗粒团聚与沉降行为的影响,探讨了天然胶体及o-MWCNTs的浓度对nZnO颗粒团聚粒径、团聚速率及沉降行为的作用.结果表明,nZnO在天然水体中会发生明显沉降,相比去除天然胶体的天然水而言,天然胶体的存在显著减少了nZnO的沉降.这主要归因于nZnO-天然胶体颗粒间的作用能垒高于nZnO-nZnO颗粒间的作用能垒,使得天然胶体的存在降低了nZnO-nZnO之间的颗粒碰撞效率,从而促进nZnO悬浮.o-MWCNTs对nZnO在天然水体中沉降行为的影响与天然胶体密切相关.相比于nZnO的单独沉降,在不过膜天然水中(含天然胶体),低浓度o-MWCNTs的存在增加了颗粒间的团聚速率,从而促进nZnO的沉降,而高浓度o-MWCNTs降低了颗粒间的团聚速率和团聚体粒径,从而降低了nZnO的沉降.而在过膜天然水中(不含天然胶体),o-MWCNTs的存在显著降低了颗粒间的团聚粒径和团聚速率,从而降低了nZnO的沉降,且o-MWCNTs的浓度越高,对nZnO悬浮稳定性的促进作用越明显.     

Evaluation of the adsorption potential of titanium dioxide nanoparticles for arsenic removal

The adsorption potential of titanium dioxide (TiO2) nanoparticles for removing arsenic from drinking water was evaluated. Pure and iron-doped TiO2 particles are synthesized via sol-gel method. The synthesized TiO2 nanoparticles were then immobilized on ordinary sand for adsorption studies. Adsorption isotherms were conducted on the synthesized nanoparticles as well as the sand coated with TiO2 nanoparticles under varying conditions of air and light, namely, the air-sunlight (A-SL), air-light (AL), air-dark (AD) and nitrogen-dark (ND). X-Ray diffraction (XRD) analysis showed that the pure and the iron-doped TiO2 nanoparticles were in 100% anatase crystalline phase with crystal sizes of 108 and 65 nm, respectively.Adsorption of arsenic on the three adsorbents was non-linear that could be described by the Freundlich and Langmuir adsorption models. Iron doping enhanced the adsorption capacity of TiO2 nanoparticle by arresting its grain growth and making it visible light responsive resulting in a higher affinity for arsenic. Similarly, the arsenic removal by adsorption on the sand coated with TiO2 nanoparticles was the highest among the three types of sand used. In all cases, As(V) adsorbed more compared with As(III). Solution pH appeared to be the most important factor in controlling the amount of arsenic adsorbed.     

负载型二氧化钛光催化降解苯胺

以紫外灯为光湖，在圆柱型光反应器中，负载在镍网上的ＴｉＯ２为催化剂，研究了水中苯胺光催化剂降解行为，结果表明苯胺的降解动力学可用Ｌａｎｇｍｕｉｒ－Ｈｉｎｓｈｅｌｗｏｏｄ方程来描述，对苯胺的浓度、介质ｐＨ、液体流速、氧气浓度和外加Ｈ２Ｏ２等因素对光催化反应的影响进行了研究，并以实验现象予以解释。     

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.     

我国部分地区自来水和不同水体中的PFOS污染

采用高效液相色谱/质谱仪联机选择离子监测(LC/MS-SIM, m/z = 499)方法,测定了我国部分城市自来水、地面水、地下水和海水中的全氟辛磺酸(PFOS)含量.从全部样品中均检测到PFOS,表明我国境内水环境中普遍存在着PFOS污染.被调查部分城市自来水、海水和远离人类活动地区的水中PFOS浓度大多数低于1ng/L,容易受到生活污水和工业废水污染的水中PFOS浓度范围为1.50～44.6ng/L.     

Assessing the effect of different natural dissolved organic matters on the cytotoxicity of titanium dioxide nanoparticles with bacteria

Titanium dioxide nanoparticles(TiO_2 NPs) are among the most widely manufactured nanomaterials on a global scale. However, prudent and vigilant surveillance, incumbent upon the scientific community with the advent of new technologies, has revealed potentially undesirable effects of TiO_2 NPs on biological systems and the natural environment during their application and discharge. Such effects are likely best evaluated by first assessing the fate of the TiO_2 NPs in natural environments. In this study, the effects of terrestrial humic acid(HA) and tannic acid(TA), two major members of the collective:dissolved organic matter(DOM), on the cytotoxicity of TiO_2 NPs to Escherichia coli were investigated in the presence and absence of natural sunlight. Qualitative(transmission electron microscopy(TEM)) and quantitative(LC50) analyses were employed in this study. In addition, the production of reactive oxygen species(ROS) in the form of UOH was further assessed—as HA or TA increased the production of ROS decreased. The inhibition of bacterial viability in the light treatment groups, with respective treatment organics at concentrations of 10 ppm, was less in TA than in terrestrial HA. SAS was used to analyze the treatment effect of individual factors of light irradiation, DOM, and concentration of TiO_2 NPs.     

Effects of reductive inorganics and NOM on the formation of chlorite in the chlorine dioxide disinfection of drinking water

Chlorine dioxide (ClO₂) disinfection usually does not produce halogenated disinfection by-products, but the formation of the inorganic by-product chlorite (ClO₂^–) is a serious consideration. In this study, the ClO₂^– formation rule in the ClO₂ disinfection of drinking water was investigated in the presence of three representative reductive inorganics and four natural organic matters (NOMs), respectively. Fe²⁺ and S^2– mainly reduced ClO₂ to ClO₂^– at low concentrations. When ClO₂ was consumed, the ClO₂^– would be further reduced by Fe²⁺ and S^2–, leading to the decrease of ClO₂^–. The reaction efficiency of Mn²⁺ with ClO₂ was lower than that of Fe²⁺ and S^2–. It might be the case that MnO₂ generated by the reaction between Mn²⁺ and ClO₂ had adsorption and catalytic oxidation on Mn²⁺. However, Mn²⁺ would not reduce ClO₂^–. Among the four NOMs, humic acid and fulvic acid reacted with ClO₂ actively, followed by bovine serum albumin, while sodium alginate had almost no reaction with ClO₂. The maximum ClO₂^– yields of reductive inorganics (70%) was higher than that of NOM (around 60%). The lower the concentration of reductive substances, the more ClO₂^– could be produced by per unit concentration of reductive substances. The results of the actual water samples showed that both reductive inorganics and NOM played an important role in the formation of ClO₂^– in disinfection.     

Pilot study on bromate reduction in ozonation of water with low carbonate alkalinities by carbon dioxide

A pilot study was carried out to explore the application of carbon dioxide for pH depression in a bubble column and its ability to inhibit bromate formation for water with a low alkalinity. Results showed that in the absence of ammonia, CO2 was capable of reducing bromate 38.0%–65.4% with one-unit pH depression. CO2 caused a slightly lower bromate reduction (4.2%) than did H2SO4 when the pH was depressed to 7.4, and a more a pronounced lower reduction (8.8%) when the pH was depressed to 6.9. In the presence of 0.20 mg/L-N ammonia, bromate was largely inhibited with 73.9% reduction. When the pH was depressed to 7.4, CO2 and H2SO4 showed an 11.3% and 23.5% bromate reduction respectively, demonstrating that the joint use of CO2 and ammonia might be a plausible strategy of blocking all three bromate formation pathways. CO2 could be applied through the aeration diffuser together with ozone gas, resulting in a similar bromate reduction compared with the premixing method through Venturi mixer.     

水足迹视角下黄土高原经济林果扩张的水安全风险分析——以苹果种植为例

以苹果为主的黄土高原经济林果种植规模持续扩张,耗水量不断增多,潜在的水安全风险增大。量化苹果生产水足迹,讨论苹果生产扩张带来的水安全风险,对科学指导未来黄土高原苹果健康发展具有重要意义。本文基于ArcGIS和CROPWAT软件,选取2000—2019年黄土高原44个市（州）,探究了苹果水足迹的时空分布规律及水安全风险。结果表明：2000—2019年,黄土高原苹果种植面积增长了1.3倍,产量增长了3.1倍,呈“北移西扩”的发展趋势;苹果绿水足迹占比的空间分布与降雨量基本一致,从东南向西北递减,蓝水足迹空间分布正好相反;苹果水足迹总量从74.42亿m³增长到108.04亿m³,占农业耗水量的比例由42.78%提升至65.63%,灰水足迹占比高达13.88%,黄土高原苹果生产面临严峻的水安全风险。因此,应适度控制黄土高原苹果种植规模的进一步扩张。本文可为评价黄土高原苹果种植规模扩张背后的水安全风险提供依据。     

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.     

Integrated water resources management for emergency situations: A case study of Macau

Integrated urban water management (IUWM) is a useful tool that can be used to alleviate water resource shortages in developing regions like Macau, where 98% of the raw water comes from mainland China. In Macau, scarce water resources deteriorate rapidly in emergency situations, such as accidental chemical spills upstream of the supply reservoir or salty tides. During these times, only the water from the two freshwater reservoirs in Macau can be used. In this study, we developed urban water management optimization models that integrated the raw water supply from the two reservoirs with various proposed governmental policies (wastewater reuse, rainwater collection, and water saving). We then determined how various water resource strategies would influence the urban water supply in Macau in emergency situations. Our results showed that, without imported raw water, the water supply from only the two Macau reservoirs would last for 7.95 days. However, when all the government policies were included in the model, the supply could be extended to 13.79 days. Out of the three non-conventional water resources, wastewater reuse is the most beneficial for increasing the Macau water supply, and rainwater collection also has great potential.     

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.     

Synthesis of novel adsorbent by intercalation of biopolymer in LDH for the removal of arsenic from synthetic and natural water

This study focuses on the synthesis of nanocomposites named CCA and CZA that were prepared by the incorporation of cellulose(CL) in the Ca/Al and Zn/Al layered double hydroxide(LDH),respectively.These materials were then used for the uptake of As(Ⅲ)and As(V) from aqueous medium.Characterization of both nanocomposites(CCA and CZA) was done using FTIR and Raman analysis to identify the functional groups, N_2 adsorption-desorption isotherms to determine the specific surface area and pore geometry and XPS analysis to obtain the surface atomic composition.Some other characters were investigated using simultaneous TGA and DTA and elemental chemical analysis(CHNS/O).The crystallinity of the prepared nanocomposites was displayed by XRD patterns.Furthermore,the sheet-like structure of the LDHs and the irregularity of surface morphology with porous structure were observed by TEM and SEM microphotographs.Optimization of maximum adsorption capacity was adjusted using different parameters including pH,contact time and adsorbent dosage.The pseudo-second-order model was in good fitting with kinetics results.The adsorption isotherm results showed that CZA exhibits better adsorption capacity for As(Ⅲ) than CCA and the Langmuir isotherm model described the data well for both nanocomposites.Thermodynamic studies illustrated the endothermic nature of CCA and exothermic nature on CZA,as well as the fact that the adsorption process is spontaneous.A real water sample collected from well located in Gabes(Tunisia),has also been treated.The obtained experimental results were confirmed that these sorbents are efficient for the treatment of hazardous toxic species such as.     

城市水价研究的理论与实践——以济南市自来水价研究为例

在分析水资源价值的基础上,重点阐明合理的水资源价格应由水资源价值、供水成本、外部成本和机会成本四部分构成;进而针对目前济南市水价中存在的问题,提出合理的水资源费征收标准应按地表水水资源费、地下水水资源费和引黄水水资源费分别制定,以使水资源费全面体现水资源价值;污水处理费征收标准应提高到包括工程费、服务费和资本费在内的水平,以补偿污水处理成本;改革现行的计划定价法和成本定价法这两种不合理的水价制定方法;实行季节水价、两部制水价和阶梯式计量水价,使水价反映水资源开发利用成本和条件的变化,以促进全社会节约用水。     

水质参数对功能化石墨烯在水中凝聚行为的影响

采用动态光散射技术研究了不同价态阳离子、富里酸（FA）等对两种功能化石墨烯（FG）悬浮凝聚行为的影响机制.结果表明：FG分别在含不同浓度Na⁺、Ca²⁺和La³⁺的电解质溶液中,其临界聚集浓度（CCC）值范围为221~263,3~4,0.05~0.07mmol/L,符合经典的DLVO理论与Schulze-Hardy法则.5种FA亚组分均可显著抑制FG在水体中的凝聚,加入5mg/L的FA亚组分后,在不同浓度的Ca²⁺和La³⁺的电解质溶液中,FG-OH （FG-COOH）的CCC值分别增大12.5%~37.5%（3.2%~4.5%）和4.2%~25.7%（10%~46%）.FG的CCC值与FA亚组分的C、H含量和H/C比显著正相关（P<0.05）,与O含量、O/C比和羧基C含量显著负相关（P<0.05）.差分荧光光谱研究表明随着FG的加入,FA的荧光强度逐渐降低,二者发生相互作用.     

水资源与社会经济发展要素时空匹配特征——以张家口为例

水资源短缺已成为制约区域经济社会发展的重要因素,协调水资源与社会经济关系是水资源可持续利用的关键。以张家口为例,采用洛伦兹基尼系数和不均衡指数模型对水资源与社会经济发展要素的时空匹配特征进行研究,结果表明：2004—2015年张家口水资源与人口、耕地面积分布处于“匹配比较合理”和“相对匹配”状态,水资源与经济布局匹配呈现出由“完全不匹配”状态逐渐转变为“相对不匹配”状态。在空间匹配演化方面,水资源与人口、耕地面积的匹配度变化不大。水资源与经济匹配结果表明在水资源禀赋越差的地区,经济增速越快,水资源与经济的空间匹配状况越差。张家口水资源与社会经济发展要素时空匹配特征研究,对于指导区域水资源合理开发利用具有重要的现实意义。     

Water pricing towards sustainability of water resources: a case study in Beijing

The role of water pricing for managing water resources is widely recognized in many areas of the world because of the increasing scarcity of water resources, a high competition between water uses and environmental degradation. Based on the analysis of cost of water, this paper explores which types of cost should be reflected in the water pricing enhancing the sustainability of water resources. The principle of full cost pricing in which the cost should include supply cost, opportunity cost and externalities is proposed as a means to achieve the sustainability of water resources. In a case study of Beijing, low water price is analyzed as one reason for unsustainable water consumption. Thus water pricing justified is necessary and pressing. It is proposed to justify water price in phased manner and eventually towards full cost pricing. The assessment of impacts on water resources by raising water price shows water pricing could alleviate the conflict between water supply and demand. This paper concludes that water pricing can play an effective role in enhancing the sustainability of water resources in Beijing.     

Evaluating the effectiveness of marine actinobacterial extract and its mediated titanium dioxide nanoparticles in the degradation of azo dyes

Aim of the present study was to synthesize titanium dioxide nanoparticles （YiO2 NPs） from marine actinobacteria and to develop an eco-friendly azo-dye degradation method. A total of five actinobacterial isolates were isolated from Chennai marine sediments, Tamilnadu, India and analyzed for the synthesis of TiO2 NPs using titanium hydroxide. Among these, the isolate PSV 3 showed positive results for the synthesis of TiO2 NPs, which was confirmed by UV analysis. Further characterization of the synthesized TiO2 NPs was done using XRD, AFM and FI＇-IR analysis. Actinobacterial crude extract and synthesized TiO2 NPs was found efficient in degrading azo dye such as Acid Red 79 （AR-79） and Acid Red 80 （AR-80）. Degradation percentage was found to be 81% for AR-79, 83% for AR-80 using actinobacterial crude extract and 84% for AR-79, 85% for AR-80 using TiO2 NPs. Immobilized actinobacterial ceils showed 88% for AR-79 and 81% for AR- 80, dye degrading capacity. Degraded components were characterized by FT-IR and GC-MS analysis. The phytotoxicity test with 500 μg/mL of untreated dye showed remarkable phenotypic as well as cellular damage to Tagetes erecta plant. Comparatively no such damage was observed on plants by degraded dye components. In biotoxicity assay, treated dyes showed less toxic effect as compared to the untreated dyes.