Electrospun and functionalized PVDF/PAN nanocatalyst-loaded composite for dechlorination and photodegradation of pesticides in contaminated water

A novel approach for the electrospinning and functionalization of nanocatalyst-loaded polyvinylidene fluoride/polyacrylonitrile (PVDF/PAN) composite grafted with acrylic acid (AA; which form polyacrylic acid (PAA) brush) and decorated with silver (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd) designed for the dechlorination and photodegradation of pesticides was carried out. PAN was used both as a nitrogen dopant as well as a co-polymer. Smooth nanofibers were obtained by electrospinning a solution of 12:2 wt.% PVDF/PAN blend using dimethylformamide (DMF) as solvent. The nanofibers were grafted with AA by free-radical polymerization using 2,2′azobis(2-methylpropionitrile) (AIBN) as initiator. Both bimetallic iron–palladium (Fe–Pd) and titania (TiO₂) nanoparticles (NP) were anchored on the grafted nanofibers via the carboxylate groups by in situ and ex situ synthesis. The Fe–Pd and nitrogen-doped TiO₂ nanoparticles were subsequently used for dechlorination and oxidation of target pollutants (dieldrin, chlorpyrifos, diuron, and fipronil) to benign products. Structural and chemical characterizations of the composites were done using various techniques. These include surface area and porosity analyzer (ASAP) using the technique by Brunner Emmett Teller (BET), Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM) analyses were done. After dechlorination, the transformation products (TPs) for dieldrin, chlorpyrifos, diuron, and fipronil were obtained and identified using two-dimensional gas chromatography (time-of-flight) with a mass spectrometer detector (GCxGC-TOFMS). Analysis of total organic carbon (TOC) was carried out and used to extrapolate percentage mineralization. Experimental results showed that dechlorination efficiencies of 96, 93, 96, and 90 % for 1, 2, 2, and 3 h treatment period were respectively achieved for 5 ppm solutions of dieldrin, chlorpyrifos, diuron, and fipronil. The dechlorination of dieldrin, diuron, and fipronil follows first-order kinetics while that of chlorpyrifos followed pseudo-first order. Mineralization performance of 34 to 45 % were recorded when Fe–Pd was used, however upon electrospinning, doping, and grafting (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd composite); it significantly increased to 99.9999 %. This composite reveals great potential for dechlorination and mineralization of pesticides in contaminated water.     

The effect of titanium dioxide nanoparticles on neuroinflammation response in rat brain

Titanium dioxide nanoparticles (TiO₂ NPs) are widely used for their whiteness and opacity in several applications such as food colorants, drug additives, biomedical ceramic, and implanted biomaterials. Research on the neurobiological response to orally administered TiO₂ NPs is still limited. In our study, we investigate the effects of anatase TiO₂ NPs on the brain of Wistar rats after oral intake. After daily intragastric administration of anatase TiO₂ NPs (5–10 nm) at 0, 50, 100, and 200 mg/kg body weight (BW) for 60 days, the coefficient of the brain, acethylcholinesterase (AChE) activities, the level of interleukin 6 (IL-6), and the expression of glial fibrillary acidic protein (GFAP) were assessed to quantify the brain damage. The results showed that high-dose anatase TiO₂ NPs could induce a downregulated level of AChE activities and showed an increase in plasmatic IL-6 level as compared to the control group accompanied by a dose-dependent decrease inter-doses, associated to an increase in the cerebral IL-6 level as a response to a local inflammation in brain. Furthermore, we observed elevated levels of immunoreactivity to GFAP in rat cerebral cortex. We concluded that oral intake of anatase TiO₂ NPs can induce neuroinflammation and could be neurotoxic and hazardous to health.     

Combination of biochar amendment and phytoremediation for hydrocarbon removal in petroleum-contaminated soil

Remediation of soils contaminated with petroleum is a challenging task. Four different bioremediation strategies, including natural attenuation, biochar amendment, phytoremediation with ryegrass, and a combination of biochar and ryegrass, were investigated with greenhouse pot experiments over a 90-day period. The results showed that planting ryegrass in soil can significantly improve the removal rate of total petroleum hydrocarbons (TPHs) and the number of microorganisms. Within TPHs, the removal rate of total n-alkanes (45.83 %) was higher than that of polycyclic aromatic hydrocarbons (30.34 %). The amendment of biochar did not result in significant improvement of TPH removal. In contrast, it showed a clear negative impact on the growth of ryegrass and the removal of TPHs by ryegrass. The removal rate of TPHs was significantly lower after the amendment of biochar. The results indicated that planting ryegrass is an effective remediation strategy, while the amendment of biochar may not be suitable for the phytoremediation of soil contaminated with petroleum hydrocarbons.     

Polycyclic aromatic hydrocarbons and trace metals in mosque’s carpet dust of Riyadh,Saudi Arabia,and their health risk implications

The main objectives of this work were to identify and determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) and trace metals in carpet dust samples from various mosques of the city of Riyadh and to assess the health risks associated with the exposure to these pollutants. Therefore, 31 samples of mosque’s carpet dust from Riyadh were collected. The results showed that 14 PAHs were present in the dust samples with concentrations ranged from 90 to 22,146 ng g^?1 (mean = 4096 ± 4277 ng g^?1) where low molecular weight compounds were dominant. The presence of PAHs were in the order of naphthalene > chrysene and benzo(b)fluoranthene > benzo(a)pyrene > acenaphthene and benzo(k)fluoranthene > pyrene and the absence of indeno(1,2,3-cd)pyrene and dibenz(a,h)anthracene. The diagnostic ratio coupled with principle component analysis (PCA) revealed mix sources of petrogenic from traffic, stack emission, and pyrogenic inputs from essence and perfumed wood burning. Trace metals were significant in the dust samples, and their concentrations decrease in the order of Zn, Mn, Cu, Cr, Pb, Ni, and V where Zn being the highest (94.4 ± 91.5 μg g^?1) and indium was the lowest (1.9 ± 9.3 μg g^?1). The trace metals were major in southern and central parts of Riyadh and followed the order of central Riyadh > southern Riyadh > western Riyadh > eastern Riyadh > northern Riyadh. Estimated risk based on the total PAHs was found to be 4.30 × 10^?11 for adult and 1.56 × 10^?11 for children. Elemental non-cancer risk for adults ranged from 7.9 × 10^?4 for Co to 7.58 × 10^?1 for Li and for children ranged from 3.70 × 10^?3 for Co to 3.54 for Li. Policy implication and mitigations of PAHs in Riyadh and Saudi Arabia were highlighted.     

Emerging trends in photodegradation of petrochemical wastes: a review

Various human activities like mining and extraction of mineral oils have been used for the modernization of society and well-beings. However, the by-products such as petrochemical wastes generated from such industries are carcinogenic and toxic, which had increased environmental pollution and risks to human health several folds. Various methods such as physical, chemical and biological methods have been used to degrade these pollutants from wastewater. Advance oxidation processes (AOPs) are evolving techniques for efficient sequestration of chemically stable and less biodegradable organic pollutants. In the present review, photocatalytic degradation of petrochemical wastes containing monoaromatic and poly-aromatic hydrocarbons has been studied using various heterogeneous photocatalysts (such as TiO₂, ZnO and CdS. The present article seeks to offer a scientific and technical overview of the current trend in the use of the photocatalyst for remediation and degradation of petrochemical waste depending upon the recent advances in photodegradation of petrochemical research using bibliometric analysis. We further outlined the effect of various heterogeneous catalysts and their ecotoxicity, various degradation pathways of petrochemical wastes, the key regulatory parameters and the reactors used. A critical analysis of the available literature revealed that TiO₂ is widely reported in the degradation processes along with other semiconductors/nanomaterials in visible and UV light irradiation. Further, various degradation studies have been carried out at laboratory scale in the presence of UV light. However, further elaborative research is needed for successful application of the laboratory scale techniques to pilot-scale operation and to develop environmental friendly catalysts which support the sustainable treatment technology with the “zero concept” of industrial wastewater. Nevertheless, there is a need to develop more effective methods which consume less energy and are more efficient in pilot scale for the demineralization of pollutant.     

Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ¹⁸O_P) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L^?1 NaHCO₃ (pH = 8.5), 0.1 mol L^?1 NaOH and 1 mol L^?1 HCl) of agricultural soils from the Beijing area. The δ¹⁸O_P results of the water extracts and NaHCO₃ extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ¹⁸O_P value of the water extracts and NaHCO₃ extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ¹⁸O_P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ¹⁸O_P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ¹⁸O_p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.     

Wastewater reuse: modeling chloroform formation

The chloroform is a substance that presents a significant risk to or via the aquatic environment. Thus, the emissions, discharges and losses of this substance need to be controlled during wastewater disinfection for reclamation and reuse purposes. Due to its carcinogenetic potential, multiple studies have been carried out on drinking and surface/natural waters but less consideration has been directed to the wastewater disinfection. The focus of this work studied the formation of chloroform during chlorination in prepared waters or artificial matrices that intended to simulate wastewaters stored in landscape ponds for green areas irrigation. The relation between reaction time, chlorine dose, and chloroform formation and the variation of the dissolved organic carbon (DOC) content during the reaction was assessed. A two-variant model was proposed to simulate breakpoint chlorination practices (when chlorine dose is equal or lower than chlorine demand) and super chlorination techniques (when chlorine dose tends to surpass chlorine demand). The model was validated by the application of actual data from working conditions of six wastewater treatment plants located in Algarve, Portugal, including other data obtained in previous research studies that were not used in the model development, and by comparing the predicted values with real measured ones.     

Molecular tools for bathing water assessment in Europe: Balancing social science research with a rapidly developing environmental science evidence-base

The use of molecular tools, principally qPCR, versus traditional culture-based methods for quantifying microbial parameters (e.g., Fecal Indicator Organisms) in bathing waters generates considerable ongoing debate at the science–policy interface. Advances in science have allowed the development and application of molecular biological methods for rapid (~2 h) quantification of microbial pollution in bathing and recreational waters. In contrast, culture-based methods can take between 18 and 96 h for sample processing. Thus, molecular tools offer an opportunity to provide a more meaningful statement of microbial risk to water-users by providing near-real-time information enabling potentially more informed decision-making with regard to water-based activities. However, complementary studies concerning the potential costs and benefits of adopting rapid methods as a regulatory tool are in short supply. We report on findings from an international Working Group that examined the breadth of social impacts, challenges, and research opportunities associated with the application of molecular tools to bathing water regulations.     

Acute and chronic ecotoxicity of carbaryl with a battery of aquatic bioassays

The ecotoxic effects of carbaryl (carbamate insecticide) were investigated with a battery of four aquatic bioassays. The nominal effective concentrations immobilizing 50% of Daphnia magna (EC50) after 24 and 48 h were 12.76 and 7.47 µg L^?1, respectively. After 21 days of exposure of D. magna, LOECs (lowest observed effect concentrations) for cumulative molts and the number of neonates per surviving adult were observed at carbaryl concentration of 0.4 µg L^?1. An increase of embryo deformities (curved or unextended shell spines) was observed at 1.8 and 3.7 µg L^?1, revealing that carbaryl could act as an endocrine disruptor in D. magna. Other bioassays of the tested battery were less sensitive: the IC50-72h and IC10-72h of the algae Pseudokirchneriella subcapitata were 5.96 and 2.87 mg L^?1, respectively. The LC50-6d of the ostracod Heterocypris incongruens was 4.84 mg L^?1. A growth inhibition of H. incongruens was registered after carbaryl exposure and the IC20-6d was 1.29 mg L^?1. Our results suggest that the daphnid test sensitivity was better than other used tests. Moreover, carbaryl has harmful and toxic effects on tested species because it acts at low concentrations on diverse life history traits of species and induce embryo deformities in crustaceans.     

Analysis of waste management issues arising from a field study evaluating decontamination of a biological agent from a building

The Bio-response Operational Testing and Evaluation (BOTE) Project was a cross-government effort designed to operationally test and evaluate a response to a biological incident (release of Bacillus anthracis [Ba] spores, the causative agent for anthrax) from initial public health and law enforcement response through environmental remediation. The BOTE Project was designed to address site remediation after the release of a Ba simulant, Bacillus atrophaeus spp. globigii (Bg), within a facility, drawing upon recent advances in the biological sampling and decontamination areas. A key component of response to a biological contamination incident is the proper management of wastes and residues, which is woven throughout all response activities. Waste is generated throughout the response and includes items like sampling media packaging materials, discarded personal protective equipment, items removed from the facility either prior to or following decontamination, aqueous waste streams, and materials generated through the application of decontamination technologies. The amount of residual contaminating agent will impact the available disposal pathways and waste management costs. Waste management is an integral part of the decontamination process and should be included through “Pre-Incident” response planning. Overall, the pH-adjusted bleach decontamination process generated the most waste from the decontamination efforts, and fumigation with chlorine dioxide generated the least waste. A majority of the solid waste generated during pH-adjusted bleach decontamination was the nonporous surfaces that were removed, bagged, decontaminated ex situ, and treated as waste. The waste during the two fumigation rounds of the BOTE Project was associated mainly with sampling activities. Waste management activities may represent a significant contribution to the overall cost of the response/recovery operation. This paper addresses the waste management activities for the BOTE field test.Implications: Management of waste is a critical element of activities dealing with remediation of buildings and outdoor areas following a biological contamination incident. Waste management must be integrated into the overall remediation process, along with sampling, decontamination, resource management, and other important response elements, rather than being a stand-alone activity. The results presented in this paper will provide decision makers and emergency planners at the federal/state/tribal/local level information that can be used to integrate waste management into an overall systems approach to planning and response activities.