This paper focuses on the recent advances on radiolysis-assisted shape-controlled synthesis of noble metal nanostructures. The techniques and protocols for producing desirable shapes of noble metal nanoparticles are discussed through introducing the critical parameters which can influence the nucleation and growth mechanisms. Nucleation rate plays a vital role on the crystallinity of seeds while growth rate of different seeds' facets determines the final shape of resultant nanoparticles. Nucleation and growth rate both can be altered with factors such as absorbed dose, capping agents, and experimental environment condition to control the final shape. Remarkable physical and chemical properties of synthesized noble metal nanoparticles by controlled morphology have been systematically evaluated to fully explore their applications.
Photocatalytic remediation of industrial water pollution has courted intense attention lately due to its touted green approach. In this respect, Keggin-based polyoxometalates (POMs) as green solid acids in photocatalytic reaction possess superior qualities, viz. unique photoinduced charge-transfer properties, strong photooxidative-photoreductive ability, high chemical and thermal stability, and so forth. Unfortunately, it suffers from a large bandgap energy, low specific surface area, low recoverability, and scarce utilization in narrow absorption range. Therefore, the pollutant degradation performance is not satisfactory. Consequently, multifarious research to enhance the photocatalytic performance of Keggin-based POMs were reported, viz. via novel modifications and functionalizations through a variety of materials, inclusive of, inter alia, metal oxides, transition metals, noble metals, and others. In order to advocate this emerging technology, current review work provides a systematic overview on recent advancement, initiated from the strategized synthetic methods, followed by hierarchical enhancement and intensification process, at the same time emphasizes on the fundamental working principles of Keggin-based POM nanocomposites. By reviewing and summarizing the efforts adopted global-wide, this review is ended with providing useful outlooks for future studies. It is also anticipated to shed light on producing Keggin-based POM nanocomposites with breakthrough visible- and solar-light-driven photocatalytic performance against recalcitrant organic waste.
Waste residues and acidic effluents (post-processing of E-waste) released into the local surroundings cause perilous environmental threats and potential risks to human health. Only limited research and information are available toward the sustainable management of waste residues generated post resource recovery of E-waste components. In the present study, the manual processing of obsolete computer (keyboard, monitor, CPU, and mouse) and chemical leaching of waste printed circuit boards (WPCBs) (motherboard, hard drive, DVD drive, and power supply) were performed for urban mining. The toxicity characteristics of typical pollutants in the residues of the WPCBs (post chemical leaching) were studied by toxicity characteristics leaching procedure (TCLP) test. Manual dismantling techniques resulted in an efficient urban mining concept with an overall average profit estimation of INR 2513.73/US$ 34.59. The chemical leaching of WPCBs showed a high concentration of metal leaching like Cu (229662 ± 575.3 mg/kg) and Pb (36785.67 ± 13.07 mg/kg) in the motherboard after stripping epoxy coating. The toxicity test revealed that the concentration of Cu (245.746 ± 0.016 mg/l) in the treated waste residue and Cu (430.746 ± 0.0015 mg/l) and Pb (182.09 ± 0.0035 mg/l) in the non-treated waste residue exceeded the threshold limit. The concentrations of other elements As, Cd, Co, Cr, Ag, Mn, Zn, Ni, Fe, Se, and In were within the permissible limit. Hence, the waste residue stands non-hazardous except Cu and Pb. Stripping out the epoxy coating of WPCBs enhances the metal leaching concentrations. The study highlighted that efficient and appropriate E-waste urban mining has immense potential in tracing the waste scrap into secondary resources. This study also emphasized that the final processed waste residue (left unattended or discarded due to lack of appropriate skill and technology) can be taken into consideration and exploited for value-added materials.
Land exploitation for mining sector may leave a series of environmental impacts on our ecosystem if not appropriately managed. Therefore, the present study attempts to evaluate the various environmental aspects due to abandoned metal mining including former iron ore, bauxite, and tin mining lands in view of its hydrogeochemical behavior. Mine-impacted waters and sediments were ascertained from former mining ponds, mine tailings, and impacted streams for interpretation of aqueous and sediment geochemistry, major and trace elements, hydrochemical facies, chemical weathering rate and CO2 consumption, and water quality classification. Results indicated that the environmental impact of the long-abandoned iron ore mine was still evident with some high concentration of metals and acidic pH. Higher concentrations of Fe and Mn in water were noticeable in some areas while other trace elements (Pb, Zn, As, Cd, Cr, and Cu) were found below the recommended guideline values. Sediment quality reflected the trend of water quality variables mainly associated with metal(loid) elements, resulting in potential ecological risk, classified as having low to moderate risk. There were variations in terms of hydrochemical facies of the waters suggesting the influence of minerals in water. The chemical weathering rate suggests that contribution of carbonate mineral weathering was more important (up to 60%) than silicate weathering. The resulting CO2 consumption by mineral weathering was estimated to be in the range of 1.7-9.8 × 107 mol/year (former bauxite and tin mining areas can act as temporary sinks for CO2). Water quality classifications according to several chemical indices (Kelly's ratio, sodium absorption ratio, soluble sodium percentage, residual sodium carbonate, magnesium absorption ratio, and permeability index) were also discussed in regards to mine water reuse for irrigation purpose. The findings suggest that a holistic approach that integrates all important hydrogeochemical aspects is essential for a thorough evaluation of the implication of medium- to long-term mining exploitation on its surrounding ecosystems. This would be beneficial in light of restoration potential of degraded mining land so as for future mitigation strategies in the mining sector.
There is limited information on the optimal processes to remove heavy metals in greywater. A Response Surface Methodology (RSM) via the Box-Behnken Design (BBD) approach was applied in this study to investigate and optimise the process variables of activation time (1.5-2.5 h), impregnation ratio (0.25-0.75) and zinc chloride (ZnCl2) percentage (20-60%) for the removal of heavy metal ions (Cd, Cu, Pb and Ni) associated with greywater treatment. The quadratic model was chosen to describe the effects of the process variables (activation time, impregnation ratio, ZnCl2 percentage) on predicting the responses (heavy metal ions removal) with low p-values (
Sewage sludge has long been regarded as a hazardous waste by virtue of the loaded heavy metals and pathogens. Recently, more advanced technologies are introduced to make use of the nutrients from this hazardous sludge. Successful recovery of sludge's carbon content could significantly convert waste to energy and promote energy sustainability. Meanwhile, the recovery of nitrogen and trace minerals allows the production of fertilizers. This review is elucidating the performances of modern thermal treatment technologies in recovering resources from sewage sludge while reducing its environmental impacts. Exhaustive investigations show that most modern technologies are capable of recovering sludge's carbon content for energy generation. Concurrently, the technologies could as well stabilize heavy metals, destroy harmful pathogens, and reduce the volume of sludge to minimize the environmental impacts. Nevertheless, the high initial investment cost still poses a huge hurdle for many developing countries. Since the initial investment cost is inevitable, the future works should focus on improving the profit margin of thermal technologies; so that it would be more financially attractive. This can be done through process optimization, improved process design as well as the use of suitable co-substrates, additives, and catalyst as propounded in the review.
Metal nanoclusters have been considered as a new class of chemical sensors due to their unique electronic structures and the particular physicochemical properties. The interaction of N2 molecule with neutral and ionic magnesium nanoclusters Mg17q(q=0,±1), as well as neutral magnesium nanoclusters with the centrality of beryllium and calcium Mg16M (M=Be, Mg, and Ca) have been investigated using CAM-B3LYP/6-311+G(d) level of theory in the gas phase. The electronic properties of magnesium nanoclusters were significantly affected by the adsorption of N2 molecule. The NBO analysis revealed a charge transfer from the adsorbed N2 molecule to the nanocluster. Based on the adsorption energies and enthalpies, a thermodynamically favorable chemisorption process was predicted for the Mg16Ca-N2 complex. The negative value of the Gibbs free energy of Mg16Ca-N2 confirmed the spontaneous adsorption process. The estimated recovery time for Mg16Ca-N2 complex for 8-MR (0.089 s) and 4-MRs (0.075 s) illustrated a possible desorption process for N2 molecule from the surface of Mg16Ca. Our finding also revealed the Mg16Ca has the ability to use as a sensor for detection and absorption of N2 molecule.
There is a global need to use plants to restore the ecological environment. There is no systematic review of phytoremediation mechanisms and the parameters for environmental pollution. Here, we review this situation and describe the purification rate of different plants for different pollutants, as well as methods to improve the purification rate of plants. This is needed to promote the use of plants to restore the ecosystems and the environment. We found that plants mainly use their own metabolism including the interaction with microorganisms to repair their ecological environment. In the process of remediation, the purification factors of plants are affected by many conditions such as light intensity, stomatal conductance, temperature and microbial species. In addition the efficiency of phytoremediation is depending on the plants species-specific metabolism including air absorption and photosynthesis, diversity of soil microorganisms and heavy metal uptake. Although the use of nanomaterials and compost promote the restoration of plants to the environment, a high dose may have negative impacts on the plants. In order to improve the practicability of the phytoremediation on environmental restoration, further research is needed to study the effects of different kinds of catalysts on the efficiency of phytoremediation. Thus, the present review provides a recent update for development and applications of phytoremediation in different environments including air, water, and soil.
The discharge of high levels of heavy metals into the environment is of concern due to its toxicity to aquatic life and potential human health impacts. Biofiltration systems have been used in urban environments to address nutrient contamination, but there is also evidence that such systems can be effective in reducing heavy metals concentration in stormwater. However, the accumulation pattern of heavy metals and lifespan of such systems, which are important in engineering design, have not been thoroughly explored. This study investigated the accumulation patterns of lead (Pb), copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe), which are common in urban runoff, in non-vegetated filtration columns using three different types of filter media, namely sand (S), and mixtures of sand with fly ash (sand-fly ash mix, SF), and with zeolite (sand-zeolite mix, SZ). The columns were assessed in terms of infiltration rate, the mass of heavy metals accumulation at different depths, and formation of crust layer (schmutzdecke) at the surface. The results show that most of the heavy metals accumulated at the top 5-10 cm of the filter media. However, Zn was found adsorbed to a depth of 15 cm in S and SZ columns, while Mn and Fe were present in column S throughout the entire 30 cm depth of the filter media. The presence especially of Zn, Mn, and Fe in the deeper portions of the filter media before the top 5 cm layer reached its maximum adsorption capacity, hints that transport to the deeper layers is not necessarily dependent on saturation of the upper layers for these heavy metals. SF accumulated heavy metals most at the top 5 cm of the filter media layer, and retained twice the mass of heavy metals in the crust layer, compared to S and SZ columns. SF also yielded the lowest value of infiltration rate of 31 mm/h. Considering both metals accumulation and clogging potential of the filter media, the periodic maintenance of these systems is suggested to be approximately between 1.5 and 3 years.
In this study, concentrations of Cd, Ni, Pb, and Cr were determined in tobacco, tobacco smoke-condensate, and cigarette ash for selected brands used in Pakistan. Smoking apparatus was designed for metal extraction from cigarette smoke. Samples were digested through microwave digester and then analyzed by flame atomic absorption spectrophotometer (FAAS). Higher concentration of Ni was detected in imported brands than the counterparts in the local brands. Pb levels were however higher in local brands while significant concentration of Cd was observed in both brands. For Cr, the level in tobacco of local brands was higher than their emitted smoke, whereas imported brands showed higher level in smoke than in tobacco. The cigarette ash retained 65 to 75% of the metal and about 25 to 30% went into the body. While this study revealed the serious requirement to standardize the manufacturing of tobacco products, more importantly is the urgent need for stronger enforcements to put in place to alert the general population about the hazardous effects of cigarettes and the health risks associated with these toxic metals.
The microbial breakdown of chitosan, a fishery waste-based material, and its derivative cross-linked chitosans, in both non-contaminated and contaminated conditions was investigated in a laboratory incubation study. Biodegradation of chitosan and cross-linked chitosans was affected by the presence of heavy metals. Zn was more pronounced in inhibiting microbial activity than Cu and Pb. It was estimated that a longer period is required to complete the breakdown of the cross-linked chitosans (up to approximately 100 years) than unmodified chitosan (up to approximately 10 years). The influence of biodegradation on the bioavailable fraction of heavy metals was studied concurrently with the biodegradation trial. It was found that the binding behaviour of chitosan for heavy metals was not affected by the biodegradation process.
The sequential extraction procedure proposed by the European Standard, Measurements and Testing (SM&T) program, formerly the Community Bureau of Reference (BCR), was applied for partitioning of heavy metals (HMs) in river sediments collected along the course of Sungai Buloh and the Straits of Malacca in Selangor, Malaysia. Eight elements (V, Pb, Cd, Cr, Co, Ni, Cu and Zn) from seven stations (S1-S7) and at different depths were analyzed using the modified BCR Sequential Extraction Procedure (SEP) in combination with ICP-MS to obtain the metal distribution patterns in this region. The results showed that heavy metal contaminations at S2 and S3 was more severe than at other sampling sites, especially for Zn, Cu, Ni and Pb. Nevertheless, the element concentrations from top to bottom layers decreased predominantly. The samples from the Straits of Malacca (S4-S7) the highest contamination factors obtained were for Co, Zn and Pb while the lowest were found for V and Cr, similar to Sungai Buloh sediments. The sediments showed a low risk for V, Cr, Cu and Pb with RAC values of less than 10%, but medium risk for Co, Zn (except S3), Cd at S1 and S2 and Ni at S1, S3 and S5. Zn at S3 and Cd at S3-S7 showed high risk to our sediment samples. There is not any element of very high risk conditions in the selected samples.
Herein, two stable lead(II) molecular-bowl-based metal-organic frameworks and their micro- and nanosized forms with open metal sites were presented. These materials could act as Lewis acid catalysts to cyanosilylation reaction. Moreover, the catalytic performances are size-dependent, with the catalyst with nanosized form being 1 order of magnitude more efficient than those with micro- and millisized forms.
Phytoremediation is considered as a cost-effective and environmentally friendly
technique for decontaminating environments that have been contaminated with
heavy metal ions. The technique describes the use of plants and their concomitant
microbes to mitigate environmental contaminations. However, conventional
remediation techniques like chemical, thermal and physical treatment methods are
too costly, and may end of causing more contamination to the environment.
Phytoremediation practice provides a major information on the utilization of plants
and their materials in decontaminating polluted environments. Heavy metals and
other organic contaminants are among the most precarious substances released into
the environment which have an eminent level of toxicity and sturdiness of both
aquatic and terrestrial organisms. The review aimed at providing a broad
understanding of utilizing various plants and their materials in decontaminating
polluted environments with heavy metals and other organic contaminants. It also
provided the general methods used in treating the aforementioned contaminants in
an environment. The review further discussed the classes of phytoremediation like
phytoextraction, phytovolatilisation, phytostabilization, phytotransformation,
phytodegradation and phytofiltration. The generalized advantages and disadvantages
of phytoremediation were ultimately highlighted.
Increasing toxic metal content in aquatic products has become a universal burden due to the risks to aquatic organisms and human health associated with the consumption of these products. In this study, toxic metal distribution and accumulation in the organs of fish and bivalve species of economic and culinary importance from the lower reaches of the Yangtze River are examined, and the corresponding health risks are also investigated. In general, the viscera and gill show higher concentration of metals than other tissues. The order of the accumulation sequence of metals in muscle tissue of fish and bivalve is Zn > Cu > Mn > Cr > As > Hg > Pb > Cd and Mn > Zn > Cu > As > Cr > Pb > Cd > Hg respectively. Maximum accumulation of Mn (507.50 μg g-1) and Pb (0.51 μg g-1) in the gill tissues indicates the major uptake of these metals from the water column. According to the Hazard Index (HI) calculations (based on USEPA), the analyzed metals will not cause any harmful health effects to individuals for both normal and habitual fish consumers, except for Hg and As in habitual consumers, if these species are consumed at a larger amount. Compared to the Chinese Food Health Criterion and other international standards (WHO/FAO), metal concentrations in the edible muscle tissues of the studied species are lesser than the acceptable levels and found to be fit for human consumption.
In this study, performances of mesoporous Mo/Al2O3 catalysts prepared by sol-gel and post-hydrolysis methods in hydrocracking of atmospheric residual oil were compared. In addition, different methods: (i) the single step and (ii) conventional impregnation method to incorporate active metal over the mesoporous support were also investigated. For single step method, Mo/Al2O3 catalysts were synthesized directly by sol-gel and post-hydrolysis method. On the other hand, the impregnation method was a two step procedure which involved the production of alumina via sol-gel or post-hydrolysis method and followed by respective Mo impregnation. In general, mesoporous Mo/Al2O3 catalysts prepared by sol-gel method resulted in relatively higher surface area (> 400 m2/g) and large pore volume (- 0.8 cm3/g). Mo/Al2O3 catalysts prepared by sol-gel method exhibited higher hydrocracking activity as well. The Mo crystal size was found to relate directly with the hydrocracking result.
Metal Organic Frameworks (MOFs) represent a promising class of metallic catalysts for reduction of nitrogen-containing contaminants (NCCs), such as 4-nitrophenol (4-NP). Nevertheless, most researches involving MOFs for 4-NP reduction employ noble metals in the form of fine powders, making these powdered noble metal-based MOFs impractical and inconvenient for realistic applications. Thus, it would be critical to develop non-noble-metal MOFs which can be incorporated into macroscale and porous supports for convenient applications. Herein, the present study proposes to develop a composite material which combines advantageous features of macroscale/porous supports, and nanoscale functionality of MOFs. In particular, copper foam (CF) is selected as a macroscale porous medium, which is covered by nanoflower-structured CoO to increase surfaces for growing a cobaltic MOF, ZIF-67. The resultant composite comprises of CF covered by CoO nanoflowers decorated with ZIF-67 to form a hierarchical 3D-structured catalyst, enabling this ZIF-67@Cu foam (ZIF@CF) a promising catalyst for reducing 4-NP, and other NCCs. Thus, ZIF@CF can readily reduce 4-NP to 4-AP with a significantly lower Ea of 20 kJ/mol than reported values. ZIF@CF could be reused over 10 cycles and remain highly effective for 4-NP reduction. ZIF@CF also efficiently reduces other NCCs, such as 2-nitrophenol, 3-nitrophenol, methylene blue, and methyl orange. ZIF@CF can be adopted as catalytic filters to enable filtration-type reduction of NCCs by passing NCC solutions through ZIF@CF to promptly and conveniently reduce NCCs. The versatile and advantageous catalytic activity of ZIF@CF validates that ZIF@CF is a promising and practical heterogeneous catalyst for reductive treatments of NCCs.
In this study, the particle size distribution and concentration of metallic elements of solvent- and water-based paint dust from bulk dust collected from dust-collecting hoppers were determined. The mean particle size diameter over a 12-week sampling period was determined using a particle size analyzer. The metals composition and concentration of the dust were determined via acid digestion technique followed by concentration analysis using inductively coupled plasma. The volume weighted mean particle diameters were found to be 0.941+/-0.016 and 8.185+/-0.201 microm for solvent- and water-based paint dust, respectively. The mean concentrations of metals in solvent-based paint dust were found to be 100+/-20.00 microg/g (arsenic), 1550+/-550.00 microg/g (copper), 15,680+/-11,780.00 microg/g (lead) and 30,460+/-10,580.00 microg/g (zinc) while the mean concentrations of metals in water-based paint dust were found to be 20.65+/-6.11 microg/g (arsenic), 9.14+/-14.65 microg/g (copper), 57.46+/-22.42 microg/g (lead) and 1660+/-1260 microg/g (zinc). Both paint dust types could be considered as hazardous since almost all of the dust particles were smaller than 10 microm. Particular emphasis on containment of solvent-based paint dust particles should be given since it was shown that they were very fine in size (<1 microm) and had high lead and zinc concentrations.
This study focuses on the fabrication and electrical characterization of a polymer composite based on nano-sized varistor powder. The polymer composite was fabricated by the melt-blending method. The developed nano-composite was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FeSEM), and energy-dispersive X-ray spectroscopy (EDAX). The XRD pattern revealed the crystallinity of the composite. The XRD study also showed the presence of secondary phases due to the substitution of zinc by other cations, such as bismuth and manganese. The TEM picture of the sample revealed the distribution of the spherical, nano-sized, filler particles throughout the matrix, which were in the 10-50 nm range with an average of approximately 11 nm. The presence of a bismuth-rich phase and a ZnO matrix phase in the ZnO-based varistor powder was confirmed by FeSEM images and EDX spectra. From the current-voltage curves, the non-linear coefficient of the varistor polymer composite with 70 wt% of nano filler was 3.57, and its electrical resistivity after the onset point was 861 KΩ. The non-linear coefficient was 1.11 in the sample with 100 wt% polymer content. Thus, it was concluded that the composites established a better electrical non-linearity at higher filler amounts due to the nano-metric structure and closer particle linkages.