High reduction of 4-nitrophenol using reduced graphene oxide/Ag synthesized with tyrosine

There is a demand for the development of environmental friendly methods for the synthesis of graphene composites. Reduced graphene oxide/silver (RGO/Ag) nanocomposites are very good catalysts. Here, we propose a simple, green method for the synthesis of RGO/Ag nanocomposite using the amino acid tyrosine as bioreductant and stabilizing agent. RGO/Ag nanocomposite was characterized by using various analytical techniques and studied for its catalytic degradation of 4-nitrophenol. Results of attenuated total reflectance Fourier transform infrared spectroscopy and Zeta potential at ?55 mV reveal the surface capping of tyrosine onto the reduced graphene oxide nanosheets. RGO/Ag nanocomposites show excellent catalytic reduction of 4-nitrophenol with NaBH₄, when compared to actual individual silver nanoparticles.     

Simultaneous leaching and carbon sequestration in constrained aqueous solutions

The behavior of metal ions’ leaching and precipitated mineral phases of metal-rich fly ash (FA) was examined in order to evaluate microbial impacts on carbon sequestration and metal immobilization. The leaching solutions consisted of aerobic deionized water (DW) and artificial eutrophic water (AEW) that was anaerobic, organic- and mineral-rich, and higher salinity as is typical of bottom water in eutrophic algae ponds. The Fe- and Ca-rich FAs were predominantly composed of quartz, mullite, portlandite, calcite, hannebachite, maghemite, and hematite. After 86 days, only Fe and Ca contents exhibited a decrease in leaching solutions while other major and trace elements showed increasing or steady trends in preference to the type of FA and leaching solution. Ca-rich FA showed strong carbon sequestration efficiency ranging up to 32.3 g CO₂/kg FA after 86 days, corresponding to almost 65% of biotic carbon sequestration potential under some conditions. Variations in the properties of FAs such as chemical compositions, mineral constituents as well as the type of leaching solution impacted CO₂ capture. Even though the relative amount of calcite increased sixfold in the AEW and the relative amount of mineral phase reached 37.3 wt% using Ca-rich FA for 86 days, chemical sequestration did not accomplish simultaneous precipitation and sequestration of several heavy metals.     

Pd nanoparticles entrapped in TiO<Subscript>2</Subscript> nanotubes for complete butane catalytic combustion at 130 °C

Air pollution by volatile organic compounds is a major health issue due to increasing industrialization and urbanization, notably in the developing countries. Cleaning organic pollutants by catalytic combustion is a potential solution, but actual methods require relatively high temperatures, thus increasing remediation costs. There is therefore a need for methods that operate at mild temperatures. Here we prepared a novel catalyst made of Pd nanoparticles entrapped in TiO₂ nanotubes by vacuum-assisted impregnation. Then, we tested this catalyst for butane combustion. The catalyst was characterized by N₂ adsorption–desorption isotherms, transmission electronic microscopy, energy-dispersive X-ray analysis coupled with a scanning transmission electron microscope, X-ray photoelectron spectroscopy and temperature programmed oxidation. Results show a complete combustion of butane at 130 °C, which is about 20 °C lower than temperatures required by actual catalysts made of Pd nanoparticles deposited on the exterior surface of TiO₂ nanotubes. Structure characterization suggests that this higher performance at lower temperature is explained by the confinement of TiO₂ nanotubes. Such a confinement could hinder the metal sintering and, in turn, facilitate the formation of PdO during oxidation on the entrapped Pd nanoparticles.     

International standardized procedures for in vivo evaluation of multi-walled carbon nanotube toxicity in water

The classical approach in ecotoxicological evaluation of chemical substances consists of conducting standardized bioassays on organism models. In this work, the potential impact of industrial multi-walled carbon nanotubes was investigated by ecotoxicological standardized procedures using aquatic organisms of different trophic levels, namely bacteria, green algae, invertebrates, fish, and amphibians. The results indicated (1) inhibition of growth in amphibians at 50 mg L^?1 and higher, and (2) no effects on daphnia and fish up to 100 mg L^?1. With the exception of algae (for which Fe deficiency is measured), it seems that the observed toxicity may be due to physiological effects in relation to the ingestion of carbon nanotubes not necessarily related to their intrinsic effects.     

Energy and environmental applications of carbon nanotubes

Energy and environment are major global issues inducing environmental pollution problems. Energy generation from conventional fossil fuels has been identified as the main culprit of environmental quality degradation and environmental pollution. In order to address these issues, nanotechnology plays an essential role in revolutionizing the device applications for energy conversion and storage, environmental monitoring, as well as green engineering of environmental friendly materials. Carbon nanotubes and their hybrid nanocomposites have received immense research attention for their potential applications in various fields due to their unique structural, electronic and mechanical properties. Here, we review the applications of carbon nanotubes (1) in energy conversion and storage such as in solar cells, fuel cells, hydrogen storage, lithium ion batteries and electrochemical supercapacitors, (2) in environmental monitoring and wastewater treatment for the detection and removal of gas pollutants, pathogens, dyes, heavy metals and pesticides and (3) in green nanocomposite design. Integration of carbon nanotubes in solar and fuel cells has increased the energy conversion efficiency of these energy conversion applications, which serve as the future sustainable energy sources. Carbon nanotubes doped with metal hydrides show high hydrogen storage capacity of around 6?wt% as a potential hydrogen storage medium. Carbon nanotubes nanocomposites have exhibited high energy capacity in lithium ion batteries and high specific capacitance in electrochemical supercapacitors, in addition to excellent cycle stability. High sensitivity and selectivity towards the detection of environmental pollutants are demonstrated by carbon nanotubes based sensors, as well as the anticipated potentials of carbon nanotubes as adsorbent to remove environmental pollutants, which show high adsorption capacity and good regeneration capability. Carbon nanotubes are employed as reinforcement material in green nanocomposites, which is advantageous in supplying the desired properties, in addition to the biodegradability. This article presents an overview of the advantages imparted by carbon nanotubes in electrochemical devices of energy applications and green nanocomposites, as well as nanosensor and adsorbent for environmental protection.     

Higher Cd adsorption on biogenic elemental selenium nanoparticles

Cadmium (Cd) is a carcinogenic metal contaminating the environment and ending up in wastewaters. There is therefore a need for improved methods to remove Cd by adsorption. Biogenic elemental selenium nanoparticles have been shown to adsorb Zn, Cu and Hg, but these nanoparticles have not been tested for Cd removal. Here we studied the time-dependency and adsorption isotherm of Cd onto biogenic elemental selenium nanoparticles using batch adsorption experiments. We measured ζ-potential values to assess the stability of nanoparticles loaded with Cd. Results show that the maximum Cd adsorption capacity amounts to 176.8 mg of Cd adsorbed per g of biogenic elemental selenium nanoparticles. The ζ-potential of Cd-loaded nanoparticles became less negative from ?32.7 to ?11.7 mV when exposing nanoparticles to an initial Cd concentration of 92.7 mg L^?1. This is the first study that demonstrates the high Cd uptake capacity of biogenic elemental selenium nanoparticles, of 176.8 mg g^?1, when compared to that of traditional adsorbents such as carboxyl-functionalized activated carbon, of 13.5 mg g^?1. An additional benefit is the easy solid–liquid separation by gravity settling due to coagulation of Cd-loaded biogenic elemental selenium nanoparticles.     

Effect of biogeochemical interactions on bioaccessibility of arsenic in soils of a former smelter site in Republic of Korea

The total concentration-based regulations for soil remediation do not consider the possible changes in bioaccessibility of remaining arsenic (As) in soils due to biogeochemical interactions after remediation. This study used As-contaminated soil and pore water samples that were collected from the rice paddy and forest/farmland located in the vicinity of a former smelter site in Republic of Korea to elucidate the changes in As bioaccessibility due to biogeochemical interactions. Bioaccessibility and chemical forms of As in soils were determined by using an in vitro method and sequential extraction, respectively, and soil microbial community was evaluated. Bioaccessibility of As in the rice paddy soil samples was higher than that in the forest/farmland soil samples. This could be attributed to relatively higher dependence of bioaccessible As in the rice paddy soils on the soil concentration of iron (Fe), aluminum, or manganese, which could lead to greater changes in bioaccessible As via reductive dissolution. The strong linear relationship (R ² = 0.90, p value ≤0.001) between the pore water As and Fe concentrations, and the greater portion of bacterial species related to reductive dissolution of Fe oxides in the rice paddies can support the higher As bioaccessibility promoted by reductive dissolution. Therefore, it is necessary to consider the potential changes in the bioaccessible As due to biogeochemical interactions in remediation of As-contaminated soils, particularly when soils are likely to be reused under reductive dissolution-promoting conditions (e.g., flooded conditions).     

Nanosensors and nanobiosensors in food and agriculture

The food and agriculture sector controls the economic growth of a developing country. The food industries have practices of growing crops, raising livestock and sea foods, food processing and packaging, regulating production and distribution with quality and safety. The process control and monitoring quality are crucial steps. Here we review nanosensors and nanobiosensors as alternative of classical quantification methods. Nanoscale dimensions of metal nanoparticles, metal nanoclusters, metal oxide nanoparticles, metal and carbon quantum dots, graphene, carbon nanotubes, and nanocomposites expand the sensitivity by signal amplification and integrate several novel transduction principles such as enhanced electrochemical, optical, Raman, enhanced catalytic activity, and superparamagnetic properties into the nanosensors. The electrochemical nanosensors, optical nanosensors, electronic nose and electronic tongue, nanobarcode technology, and wireless nanosensors have revolutionized the sensing in food and agriculture sectors with multiplex and real-time sensing capabilities. Despite previous success stories of the remunerative health sector, the approaches are transferred subsequently to food and agriculture sector; with potential application in detection of food contaminants such as preservatives, antibiotics, heavy metal ions, toxins, microbial load, and pathogens along with the rapid monitoring of temperature, traceability, humidity, gas, and aroma of the food stuff.     

Toxic mine drainage from Asia’s biggest copper mine at Malanjkhand,India

This paper has studied the environmental deterioration due to copper mining in Malanjkhand at Central-east India. No data is available on environmental degradation at the studied site although geological aspects are well studied. Mine drainage from the mines is definitively toxic. The site is also undergoing various stages of acid mine drainage (AMD) particularly from the heap leaching sites and the tailing area. AMD impacted water steam and sediment were also analysed. Results show substantial level of contamination of almost all segments of environment. Presence of elevated level of other heavy metal viz. Au, Ag, Pb, Cr, Cd, Fe, Cu and base metals like Na, K in AMD impacted water and sediments is due to metal leaching effect of AMD. Bio monitoring with the help of benthic macro invertebrates and metal accumulation in plants was also carried to know the impact of the toxic drainage. Results prove a very significant impact on the environmental health.     

Relative extraction ratio (RER) for arsenic and heavy metals in soils and tailings from various metal mines,Korea

This study focused on the evaluation of leaching behaviours for arsenic and heavy metals (Cd, Cu, Ni, Pb and Zn) in soils and tailings contaminated by mining activities. Ten representative mine soils were taken at four representative metal mines in Korea. To evaluate the leaching characteristics of the samples, eight extraction methods were adapted namely 0.1 M HCl, 0.5 M HCl, 1.0 M HCl, 3.0 M HCl, Korean Standard Leaching Procedure for waste materials (KSLP), Synthetic Precipitation Leaching Procedure (SPLP), Toxicity Characteristic Leaching Procedure (TCLP) and aqua regia extraction (AR) methods. In order to compare element concentrations as extraction methods, relative extraction ratios (RERs, %), defined as element concentration extracted by the individual leaching method divided by that extracted by aqua regia based on USEPA method 3050B, were calculated. Although the RER values can vary upon sample types and elements, they increase with increasing ionic strength of each extracting solution. Thus, the RER for arsenic and heavy metals in the samples increased in the order of KSLP < SPLP < TCLP < 0.1 M HCl < 0.5 M HCl < 1.0 M HCl < 3.0 M HCl. In the same extraction method, the RER values for Cd and Zn were relatively higher than those for As, Cu, Ni and Pb. This may be due to differences in geochemical behaviour of each element, namely high solubility of Cd and Zn and low solubility of As, Cu, Ni and Pb in surface environment. Thus, the extraction results can give important information on the degree and extent of arsenic and heavy metal dispersion in the surface environment.     

Silver nanoparticle antimicrobial activity explained by membrane rupture and reactive oxygen generation

Silver nanoparticles are widely used as antimicrobial compounds based on empirical observations. However, there is few knowledge on the mechanism ruling the antimicrobial activity and toxicity of Ag nanoparticles. Here, we investigated this mechanism. Nano-Ag was synthesised by thermal co-reduction. Mutagenicity analysis was performed using Salmonella typhimurium histidine auxotrophic strains TA 98 and TA 100 at nano-silver concentrations of 100 to 500 µg per plate. Dose-dependent analysis for reactive oxygen species generation has been performed using 2,7-dichlorofluorescein diacetate dye. Membrane integrity has been analyzed at 260 nm, before and after treatment. We also used scanning electron microscopy, membrane permeabilization test, and superoxide formation determinations. Results show that the average particle size of Ag nanoparticle is 60.4 ± 3.8 nm. The minimum inhibitory concentration of Ag nanoparticles for E.coli is 30 µg/mL; the minimum bactericidal concentration is 40 µg/mL. Ames mutagenicity tests showed negative results, which may be explained by the antimicrobial activity of nano-silver. Bacterial inner wall were indeed ruptured, and cytoplasmic content was released after 5 min of treatment in a dose-dependent manner. We thus propose that reactive oxygen generation and alteration of membrane integrity and permeability are the major mechanism of antimicrobial activity of nano-silver.     

Non-toxic,high selectivity process for the extraction of precious metals from waste printed circuit boards

● Au, Ag and Pd were recovered from WPCBs with high efficiencies. ● Au leaching is strictly dependent on WPCB size and reagent concentration. ● High Ag extraction efficiencies are achieved regardless of the WPCB size. ● Pd leaching works better with small and medium WPCB sizes. ● The leaching results suggest the possibility of selective recovery of metals. The work presented here focused on the extraction of gold (Au), silver (Ag) and palladium (Pd) from electronic waste using a solution of ammonium thiosulfate. Thiosulfate was used as a valid alternative to cyanide for precious metal extractions, due to its non-toxicity and high selectivity. The interactions between sodium thiosulfate, total ammonia/ammonium, precious metal concentrations and the particle size of the waste printed circuit boards (WPCBs) were studied by the response surface methodology (RSM) and the principal component analysis (PCA) to maximize precious metal mobilization. Au extraction reached a high efficiency with a granulometry of less than 0.25 mm, but the consumption of reagents was high. On the other hand, Ag extraction depended neither on thiosulfate/ammonia concentration nor granulometry of WPCBs and it showed efficiency of 90% also with the biggest particle size (0.50 < Ø < 1.00 mm). Pd extraction, similarly to Au, showed the best efficiency with the smallest and the medium WPCB sizes, but required less reagents compared to Au. The results showed that precious metal leaching is a complex process (mainly for Au, which requires more severe conditions in order to achieve high extraction efficiencies) correlated with reagent concentrations, precious metal concentrations and WPCB particle sizes. These results have great potentiality, suggesting the possibility of a more selective recovery of precious metals based on the different granulometry of the WPCBs. Furthermore, the high extraction efficiencies obtained for all the metals bode well in the perspective of large-scale applications.     

Nanostructured semiconducting materials for efficient hydrogen generation

Massive production of hydrogen by water decomposition triggered by a solar light active photocatalyst is a major objective in chemistry and a promising avenue to overcome the global energy crisis. The development of efficient, stable, economically viable and eco-friendly photocatalysts for hydrogen production is a challenging task. This article reviews the use of nanocomposite in three combinations: metal oxide–metal oxide semiconductor, metal–metal oxide semiconductor and metal chalcogenide–metal oxide core–shell nanostructures. These core–shell structures occur in two forms: a simple form where the photocatalyst is either in the core or the shell or in a more complex system where the core–shell structure comprises a co-catalyst deposited on a semiconducting material. We discuss the design, synthesis and development of semiconductor-based nanocomposite photocatalysts for hydrogen production. The major points are the role of catalytic active sites, the chemical nature of sacrificial agents, the effect of light sources, the variable light intensity and the energy efficiency calculation. For TiO₂-based nanocomposites, the metal oxide or metal co-catalyst loading of 1.0–3.0 wt% was optimal. TiO₂ nanotube–CuO hybrid nanocomposites produce 1,14,000 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\), whereas TiO₂/Au nanocomposites display 1,60,000 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\). For core–shell catalysts, a shell thickness of 2–20 nm was found for the best activity, and its performance is as follows: (a) CdS–NiO system produces around 19,949 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\) and (b) CuO–Cr₂O₃ as co-catalyst immobilized on TiO₂ system produces around 82,390 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\).     

Carbon nanotubes and Cu–Zn nanoparticles synthesis using hyperaccumulator plants

This article reports a novel way to synthesize carbon nanotubes and Cu/ZnO nanoparticles using metal hyperaccumulator plants. Metal hyperaccumulator plants are traditionally used for phytoremediation to clean soil polluted by toxic metals. However, the transfer of toxic metals in plant shoots and leaves is an environmental issue because animals and other living organisms feeding on plants will transfer the metals to the ecosystem. Therefore, we suggest that hyperaccumulator plants could be used to synthesize nanoparticles. Here, Brassica juncea L., a Cu-hyperaccumulator plant, was collected around a copper mine and used as a raw chemical to produce carbon nanotubes and Cu/ZnO nanoparticles. The chlorophyll in shoots of B. juncea plants was ethanol extracted to yield chlorophyllin. Cu and Zn were extracted by HNO₃ to form Cu/Zn(NO₃)₂. The chlorophyllin reacted with Cu/Zn(NO₃)₂ to form Cu/Zn chlorophyllin. Cu/ZnO nanoparticles were synthesized by direct precipitation of Cu/Zn chlorophyllin with NaOH and ethanol. The vascular bundles in B. juncea plants, which have been purified and carbonized by HNO₃, were rapidly heated to about 400°C and then they were cooled to room temperature to obtain carbon nanotubes. Results indicate that the outer diameter of carbon nanotubes was around 80 nm. Cu/ZnO nanoparticles have a Cu_0.05Zn_0.95O composition, and had a diameter of about 97 nm. Our study not only inspires the search for a new strategy on the synthesis of nanostructure from renewable natural products, but also breaks through the traditional and limited ideas about the reuse of metals by hyperaccumulator plants.     

In vitro cytotoxicity of multi-wall carbon nanotubes on human cell lines

The aim of this study was to evaluate the in vitro toxicity of two multi-wall carbon nanotubes on four different cell lines: human alveolar epithelial (A549) cells, hepatocytes (Hep 3B cells), human embryonic kidney cells, and intestinal (P407 cells) cells. The adverse effects of carbon nanoparticles were analyzed after 24 h incubation with different cell lines using the trypan blue dye exclusion method. Incubation of carbon nanotubes with different cells produced a concentration-dependent inhibition of growth of the cells. The TC₅₀ or IC₅₀ values (toxic concentration 50, i.e., concentration of particles inducing 50% cell mortality) of two nanoparticles were (1) found to be in the range 23.5–30.5 µg mL^?1, and (2) less than that of quartz (known toxic agent, 28.8–66.9 µg mL^?1), indicating the greater cytotoxic effect of carbon nanoparticles than quartz particles.     

Assessment of Young Dong tributary and Imgok Creek impacted by Young Dong coal mine,South Korea

An initial reclamation of the Young Dong coal mine site, located in northeastern South Korea, was completed in 1995. Despite the filling of the adit with limestone, acid rock drainage (ARD) enters Young Dong tributary and is then discharged to Imgok Creek. This ARD carries an average of 500 mg CaCO₃/l of mineral acidity, primarily as Fe(II) and Al. Before spring runoff, the flow of Imgok Creek is 3.3–4 times greater than that of the tributary and has an alkalinity of 100 mg CaCO₃/l, which is sufficient to eliminate the mineral acidity and raise the pH to about 6.5. From April through September 2008, there were at least two periods of high surface flow that affects the flow of ARD from the adit. Flow of ARD reaches 2.8 m³/min during spring runoff. This raised the concentrations of Fe and Al in the confluence with Imgok Creek. However, by 2 km downstream the pH of the Imgok Creek is 6.5 and only dissolved Fe is above the Korean drinking water criteria (0.30 mg/l). This suggests only a minor impact of Young Dong Creek water on Imgok Creek. Acid digestion of the sediments in Imgok Creek and Young Dong Tributary reveals considerable abundances of heavy metals, which could have a long-term impact on water quality. However, several water-based leaching tests, which better simulate the bioavailable metals pool, released only Al, Fe, Mn, and Zn at concentrations exceeding the criteria for drinking water or aquatic life.

     

Assessment of Young Dong tributary and Imgok Creek impacted by Young Dong coal mine,South Korea

An initial reclamation of the Young Dong coal mine site, located in northeastern South Korea, was completed in 1995. Despite the filling of the adit with limestone, acid rock drainage (ARD) enters Young Dong tributary and is then discharged to Imgok Creek. This ARD carries an average of 500 mg CaCO₃/l of mineral acidity, primarily as Fe(II) and Al. Before spring runoff, the flow of Imgok Creek is 3.3–4 times greater than that of the tributary and has an alkalinity of 100 mg CaCO₃/l, which is sufficient to eliminate the mineral acidity and raise the pH to about 6.5. From April through September 2008, there were at least two periods of high surface flow that affects the flow of ARD from the adit. Flow of ARD reaches 2.8 m³/min during spring runoff. This raised the concentrations of Fe and Al in the confluence with Imgok Creek. However, by 2 km downstream the pH of the Imgok Creek is 6.5 and only dissolved Fe is above the Korean drinking water criteria (0.30 mg/l). This suggests only a minor impact of Young Dong Creek water on Imgok Creek. Acid digestion of the sediments in Imgok Creek and Young Dong Tributary reveals considerable abundances of heavy metals, which could have a long-term impact on water quality. However, several water-based leaching tests, which better simulate the bioavailable metals pool, released only Al, Fe, Mn, and Zn at concentrations exceeding the criteria for drinking water or aquatic life.     

Occurrence,toxicity and adsorptive removal of the chloramphenicol antibiotic in water: a review

Chloramphenicol is a broad-spectrum bacterial antibiotic used against conjunctivitis, meningitis, plague, cholera, and typhoid fever. As a consequence, chloramphenicol ends up polluting the aquatic environment, wastewater treatment plants, and hospital wastewaters, thus disrupting ecosystems and inducing microbial resistance. Here, we review the occurrence, toxicity, and removal of chloramphenicol with emphasis on adsorption techniques. We present the adsorption performance of adsorbents such as biochar, activated carbon, porous carbon, metal–organic framework, composites, zeolites, minerals, molecularly imprinted polymers, and multi-walled carbon nanotubes. The effect of dose, pH, temperature, initial concentration, and contact time is discussed. Adsorption is controlled by π–π interactions, donor–acceptor interactions, hydrogen bonding, and electrostatic interactions. We also discuss isotherms, kinetics, thermodynamic data, selection of eluents, desorption efficiency, and regeneration of adsorbents. Porous carbon-based adsorbents exhibit excellent adsorption capacities of 500–1240 mg g^?1. Most adsorbents can be reused over at least four cycles.

     

Enhancement of photocatalytic performance in sonochemical synthesized ZnO–rGO nanocomposites owing to effective interfacial interaction

Nanocomposites composed of two or more components with desirable performance have attracted tremendous attention, mainly due to the synergic effect between the components. The effective combination of ZnO and reduced graphene oxide would lead to ameliorate the photocatalytic performance. To enhance applicability of semiconductor photocatalytic, the composites used should be good interfacial contact governed by suitable particle size distribution. Herein we aim to fabricate the different crystallize size of ZnO nanoparticles (NPs) in ZnO–reduced graphene oxide (ZnO–rGO) nanocomposites by sonochemical synthesis and subsequent facile drying treatment method. The Zn precursor, Zn(Ac)₂, with a plenty of functional groups, was used as a starting source for both reduction of graphene oxide and formation of ZnO on rGO sheets through chemical bonds without the addition of hazardous reducing agents. LiOH was chosen as an assistive reagent to enhance the complete reaction between Zn(Ac)₂ and GO in the formation of ZnO–rGO nanocomposites. More remarkably, drying condition has the great influence on the crystallize size of ZnO NPs in as-prepared ZnO–rGO nanocomposites. It is found that ZnO–rGO nanocomposites dried at ?50 °C (freeze drying) show the highest photocatalytic efficiency in the degradation of rhodamine B (RhB) as compared to ZnO–rGO nanocomposites by other drying conditions under visible-light irradiation. Correlating the crystallize size obtained by different drying temperatures with the photocatalytic activity, it is probed that the smaller crystallize size in ZnO–rGO nanocomposites enhances the interfacial contact and a chemical bonding between rGO and ZnO NPs leading to the effective separation of electrons and holes. In addition, the O ₂ ^·? anion was determined to be the main active oxidant by free radicals trapping experiment and a photodegradation mechanism of ZnO–rGO nanocomposites over rhodamine B (RhB) was proposed based on our observations.     

Seasonal Variations of Trace Metal Chemical Forms in Bed Sediments of a Karstic River in Lebanon: Implications for Self-purification

Although Lebanon has abundant water, its rivers are polluted and aquifer water mismanaged. Effective river water usage requires an understanding of the geochemistry of polluting metals in catchments. Climate is “Mediterranean”: wet winters and dry summers. Active sediment flushing is restricted to winter high discharge episodes. Except in winter, water column pollutants are removed by precipitation or sorption to the surface of static bed sediments. Hence (1) does winter flushing of contaminated sediment and replacement by clean sediment favour self purification? (2) does the distribution of metals between extractable fractions change seasonally and thereby affect metal bioavailability ? Results on the distribution of metals are reported for Fe, Pb, Zn, Cu and Cd in bed sediments from Nahr Ibrahim (a karstic river) for summer and winter. A Tessier-like sequential extraction scheme was applied to samples (< 75 μm) for five locations along a 13 km stretch to the sea. Water pH was above 8.2 at all locations implying a very low solubility for Fe. Sediment was derived from catchment soils and limestone. Total sediment Fe increased in winter at all sites following deposition of eroded soil from upstream. Cadmium, Cu and Pb derived from polluting sources; the sources of Zn were more complex. Dilution by clean sediment explained winter reductions in total Cd, Cu and Pb; Zn changes were less consistent. Iron occurred mostly (> 77 sum of fractions) in the residual fraction compared with 6– 31 for pollutants; residual Cu and Zn showed a small increase in winter whereas Cd and Pb did not change. All readily exchangeable metals decreased in winter and the carbonate bound forms predominated in both seasons. Nahr Ibrahim has a high capacity for self purification and metal resolubilisation from sediment will be limited by the solubility of carbonate forms.