A mini-review on rare earth metal-doped TiO<Subscript>2</Subscript> for photocatalytic remediation of wastewater

Titanium dioxide (TiO₂) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO₂ photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO₂ surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO₂ photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO₂ using rare earth metals describing their effect on the photocatalytic activities of the modified TiO₂ photocatalyst.     

Pesticide residues in fruits and vegetables from Pakistan: a review of the occurrence and associated human health risks

The main objective of the review is to document, assess and analyze the results of the previously reported data on levels of different pesticides in selected fruits and vegetables from Pakistan. The findings of the previous studies clearly indicated that more than 50 % of the samples were contaminated with organophosphate, pyrethroids and organochlorine pesticides. Many studies reported that among fresh fruits and vegetables tomato, apple, melon, mango, grapes, and plum crossed the FAO/WHO permissible limits for these contaminants residual levels. The comparison of other regions showed that observed levels were found above maximum residue limits (MRLs) in 50 % of the samples but were in agreement with the studies from neighboring countries like China and Bangladesh. Higher hazard risk index (HRI) values were calculated for dieldrin, methamidophos, o,p′-DDT, diazinon and p,p′-DDT in apple, mango, banana, melon, potato and onion. The review also highlights that data on pesticide residues in foodstuff is scarce which should be overcome by further extending studies from different areas of Pakistan. In order to ascertain the provision of food suitable for human consumption, it is imperative to monitor pesticides in food commodities by the country’s authorities and enforce guidelines based on permissible limits.     

Ammonia concentrations and modeling of inorganic particulate matter in the vicinity of an egg production facility in Southeastern USA

Ammonia (NH₃) is an important base gas and can react with acidic species to form atmospheric aerosols. Due to the rapid growth of poultry and swine production in the North Carolina Coastal Plain, atmospheric NH₃ concentrations across the region have subsequently increased. Ammonia concentrations and inorganic particulate matter (PM) at four ambient stations in the vicinity of an egg production facility were measured for 1 year using PM_2.5 speciation samplers with honeycomb denuders and ion chromatography (IC). Meanwhile, concentrations of NH₃ and inorganic PM in one of the egg production houses were also simultaneously measured using a gas analyzer for NH₃ and the filter pack plus IC method for inorganic PM. An equilibrium model-ISORROPIA II was applied to predict the behavior of inorganic aerosols in response to precursor gas concentrations and environmental parameters. Average ambient NH₃ concentrations varied from 10.0 to 27.0 μg/m³, and they were negatively correlated with the distances from the ambient location to the nearest egg production house exhausts. Ambient NH₃ concentrations were higher in warm seasons than in cold seasons. Measured NH₃ concentrations agreed well with ISORROPIA II model predictions at all sampling stations. For the ambient stations, there was a good agreement in particle phase NH₄ ⁺ between the model simulation and observations. For the in-house station, the model simulation was applied to correct the overestimation of particle phase NH₄ ⁺ due to gas phase NH₃ breaking through the denuders. Changes in SO₄ ^2?, NO₃ ^?, and Cl^? yield proportional changes in inorganic PM mass. Due to the abundance of NH₃ gas in the vicinity area of the monitored farm, changes in NH₃ concentrations had a small effect on inorganic PM mass. Aerosol equilibrium modeling may be used to assess the influence of precursor gas concentrations on inorganic PM formation when the measurements for some species are unavailable.     

Concentrations of Heavy Metals in Hair and Nails of Young Pakistanis: Correlation with Dietary Elements

Hair and nail samples from young Pakistani adults were separately analyzed for quantification of Cd, Cr, Cu, Ni, Pb, and Zn concentrations. The concentrations of these metals were also analyzed in commonly consumed local foods to evaluate potential correlation of hair and nail concentrations with diet. Pearson correlation coefficients ranged from 0.349 to 0.999, demonstrating diet to be a significant contributor for accumulation of heavy metals in humans.     

Alumina-supported oxime for the degradation of sarin and diethylchlorophosphate

1-(4-Chlorophenyl))-N-hydroxymethanimine and cyclohexyl-N-hydroxymethanimine were synthesized and a well-established oxime, i.e., 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride was purchased. Thereafter; all were loaded over Al₂O₃ using incipient wetness technique. The prepared systems were characterized using surface area analyzer, scanning electron microscope, energy dispersive X-ray spectrophotometer, Fourier transform infrared spectrophotometer and thermogravimetric analyzer. Kinetics of the degradation of sarin (GB) and simulant, i.e. diethylchlorophosphate (DEClP) was studied over synthesized oxime impregnated Al₂O₃ and results were compared with well reported oxime impregnated Al₂O₃. Kinetics of reaction was found to be following the pseudo first order reaction kinetics. The order of reactivity of the prepared systems was found to be cyclohexyl-N-hydroxymethanimine/Al₂O₃ > 1-(4-chlorophenyl)-N-hydroxymethanimine/Al₂O₃ > 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride/Al₂O₃ > Al₂O₃. From the reaction kinetics it was observed that the reaction with DEClP was faster than with GB. Cyclohexyl-N-hydroxymethanimine/Al₂O₃ was found to be the most reactive system with half-life of 0.94 and 15 h for DEClP and GB respectively.     

Distribution, correlation, and source apportionment of selected metals in tannery effluents, related soils, and groundwater—a case study from Multan, Pakistan

The short-term responses of H₂O₂-depletion-related parameters in moss Hypnum plumaeforme to the combined stress induced by Pb and Ni were investigated. The results showed that the Pb and Ni stress induced dose-dependent accumulation of hydrogen peroxide (H₂O₂). The increase of peroxidase (POD) activity and decrease of ascorbate peroxidase (APX) activity were observed under the combined heavy metal application. The antioxidants, ascorbate (AsA) and proline content, increased significantly when the metals were applied together. The study indicated that the cell damage caused by Pb stress was higher than that caused by Ni stress, Pb and Ni had synergistic effect in inducing the oxidative stress in moss H. plumaeforme, especially under the combination of high concentration of Ni (0.1 and 1.0 mM) and Pb. Content of proline, H₂O₂ and the activity of POD, all showed a dose-dependent increase under Pb and Ni stress, suggesting their practical value as biomarkers in moss biomonitoring, especially in the case of light pollution caused by heavy metals without the changes in the appearance of mosses.     

Monitoring of growth and physiological activities of biofilm during succession on polystyrene from activated sludge under aerobic and anaerobic conditions

The present research work monitored the successive biofilm development and its catabolic role in the degradation of polystyrene (PS). PS material was artificially colonized with biofilm by incubating it with activated sludge under aerobic and anaerobic conditions. Biofilm formation was monitored by gravimetric weight analysis, spectrophotometric absorbance technique, heterotrophic plate count, and scanning electron microscopy under aerobic and anaerobic conditions. The wet weight (1.59 and 1.17 g) and dry weight (0.41 and 0.08 g) of a biofilm showed a significant constant increase under aerobic and anaerobic conditions, respectively, from first till 9 weeks of incubation. Plate count of the selected bacteria (Escherichia coli, Salmonella typhimurium, Shigella dysenteriae, Pseudomonas aeruginosa) considerably declined (90–99 %) in the biofilm after seventh and fifth weeks of incubation under aerobic and anaerobic conditions, respectively, indicating a positive shift from pathogenic to beneficial microbial community. While most probable number index of fecal coliforms and E. coli in the sludge showed more reduction (98 and 99 %) under aerobic as compare to anaerobic conditions (86 and 91 %) after 9 weeks of biofilm formation on PS cubes. Correspondingly, the decreasing levels of chemical oxygen demand and biochemical oxygen demand (up to 73 %) showed signs of sludge digestion. Scanning electron microscope coupled with energy dispersive X-ray spectroscope revealed nature of PS media containing high carbon content. However, biofilm development proved to be involved in the biochemical transformation of the PS medium as indicated by Fourier transform infrared spectroscopy.     

Enhancement of biomethane production from cattle manure with codigestion of dilute acid pretreated lignocellulosic biomass

It is well known that dilute sulfuric acid pretreatment of the lignicellulosisc biomass is an effective approach used for the production of the ethanol. However, there are less studies on the biogas production from the pretreated lignocellulosics and hardly data available on the codigestion of cattle manure with the pretreated lignocellulosisc material. The aim of this study was to evaluate biomethane production potential of codigestion of cattle manure with dilute acid pretreated lignocellulosic biomass. Sugarcane bagasse and rice husk was pretreated with dilute sulfuric acid or phosphoric acid at 121°C for 20 minutes and subsequently subjected to anaerobic digestion alone or codigested with cattle manure.

The results showed that codigestion of 1% phosphoric acid pretreated rice husk with cattle manure led to the highest methane production of 115 Nmlg^?1VS while monodigestion of cattle manure and phosphoric acid pretreated rice husk produced 98 and 87 Nmlg^?1VS, respectively. An inhibition was observed in anaerobic digestion of sulfuric acid pretreated rice husk and sugarcane bagasse during monodigestion and codigestion with cattle manure.

The study concludes that dilute phosphoric acid pretreated lignocellulosics like sugarcane bagasse and rice husk can be used as a cosubstrate with cattle manure in anaerobic digestion for enhanced methane production. Dilute sulfuric acid pretreatment, which is effective method for the bioethanol production, causes inhibition during anaerobic digestion of the pretreated lignocellulosics.     

Currently used organophosphate and brominated flame retardants in the environment of China and other developing countries (2000–2016)

This review summarizes the environmental occurrence of new brominated flame retardants (NBFRs) and organophosphate compounds (OPs) in the environment of developing countries since 2000. The ban on the production and use of commercial formulations of polybrominated diphenyl ethers (PBDEs) have paved the way for the high use of NBFRs and OPs in consumer products to fulfill the fire safety regulations. Recent studies have shown that the ever increasing production volumes and extensive use of these chemicals as additive FRs and plasticizers have resulted into their ubiquitous occurrence in all environmental compartments. Although presumed to be safe for use and the environment, recent studies on their occurrence and persistence in the environment have raised questions. Due to the lack of awareness, research interest, and availability of technical facilities, limited scientific data is available on the occurrence of these chemicals in developing countries. In this study, we collected reported data and provide an overview of environmental occurrence of NBFRs and OPs in abiotic and biotic matrices of different developing countries. Finally, research gaps were identified with recommendations for future research work and would be useful towards the environmental management of these toxic chemicals.