Bioassimilation of lead and zinc in rabbits fed on spinach grown on contaminated soil.

Accumulation of heavy metals in the environment can pose a potential risk to living organisms. Ingestion of leafy vegetables, containing heavy metals, is one of the main routes through which these elements enter the human body. The present study was conducted to assess the accumulation of lead (Pb) and zinc (Zn) in spinach grown on metal contaminated soil, and to examine the bioassimilation of these metals in spinach-fed rabbits. Spinach grown in the fields spiked with Pb (1000 mg kg-1 soil) and Zn (150 mg kg-1 soil), was fed to the rabbits for 14 days. Concentrations of Pb and Zn in the leaves of spinach were 39.1 and 113 mg kg-1, respectively. For the assessment of Pb and Zn concentration, blood samples were collected after 24 h, 7 days and 14 days of feeding, while the essential organs, i.e. liver and kidneys of rabbits were collected at the end of feeding trials. Concentrations (mg L-1) of Pb (3.28) and Zn (7.10) increased in blood after 24 h compared to control treatment and then decreased (Pb 1.12; Zn 3.32) to a steady state with the passage of time after 7 days. A significant increase in the concentrations of Pb (1.20%, 3.95% and 5.58%) and Zn (10.7%, 6.89% and 18.4%) as compared to control treatment was also found in liver, kidney and bones of the rabbits, respectively, which was further confirmed by multivariate analysis. The highest significant values of correlation coefficient (r) were observed for blood and bones, i.e. 0.992 followed by blood and liver, i.e. 0.989. The bioassimilation of Pb in the body of rabbits was in the order of bone > kidney > liver > blood, while for Zn the order was bone > liver > kidney > blood. The bioassimilation of Pb and Zn in the blood, essential organs and bones depicted the serious health risks associated by consuming the metal contaminated vegetable.

Health risk assessment of trace metals from spinach grown on compost-amended soil.

The present study evaluates the impact of two commercially available composts on the accumulation of trace metals in soil and spinach, and their potential health risks to humans. The treatments were municipal waste compost (MC) and agricultural waste compost (AC) applied at 0.5, 1.0, and 1.5% (w/w)-with the recommended dose of NPK fertilizers (50:25:0) as a control. Trace metals concentrations (Cd, Cu, Pb, and Zn) in both composts were below the threshold level. The improved spinach yield with MC was 2.77, 16.88, and 42.34% and with AC 5.53, 17.19, and 53.38% over the control at 0.5, 1.0, and 1.5% levels, respectively. Concentrations of Cd, Cu, Pb, and Zn in spinach leaves were found higher than permissible limits at all levels of MC. However, Cu, Pb, and Zn were recorded within safe limits with AC except for Cd (which was at 1.0% and 1.5%). The daily intake of trace metals and their health risk index were found higher at elevated levels (1.0% and 1.5%) of MC and AC. The results revealed that besides all the benefits of commercial composts, they must be regularly monitored to avoid buildup of trace metals in soils and plants as well as their potential risks to human health at higher dose.

Photo-Induced Super-Hydrophilicity of Nano-Calcite @ Polyester Fabric: Enhanced Solar Photocatalytic Activity against Imidacloprid.

The present study is pertinent to photo-induced, hydrophilic, nano-calcite grown onto the mercerized surface of polyester fabric (PF), treated with UV (10-50 min) and visible light (1-5 h) in addition to its photocatalytic application. The wicking method has been employed to select the most hydrophilic sample of fabric upon irradiation. The micrographs obtained by scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy indicated the erosions occurring at the surface of nano-calcite after UV light irradiation, maintaining the crystallinity of the photocatalyst. The surface charge has been measured for as-fabricated and irradiated nano-calcite @ PF for the development of high negative zeta potential after UV light irradiation (-24.6 mV). The irradiated nano-calcite @ PF exhibited a significant change in its contact angle, and the wetting property was enhanced to a considerable extent on UV (55.32°) and visible light irradiation (79.00°) in comparison to as-fabricated nano-calcite @ PF (137.54°). The irradiated samples of nano-calcite @ PF delineated the redshift in harvesting of solar spectrum, as revealed by diffuse reflectance spectroscopy comparative spectra. Additionally, the band gap of untreated nano-calcite was found to be 3.5 eV, while UV- and visible light-irradiated PF showed a reduction in band gap up to 2.95 and 3.15 eV upon UV and visible light irradiation. The photocatalytic efficiency of mesoporous nano-calcite was evaluated by photocatalytic degradation of imidacloprid as the probe pollutant. Higher solar photocatalytic degradation of imidacloprid (94.15%) was attained by UV light-irradiated nano-calcite @ PF. The time-resolved photoluminescence study has verified the high photocatalytic activity of UV light-irradiated nano-calcite @ PF for the generation of high concentration of hydroxyl radicals. The highly efficient reusability of a nano-calcite-based solar photocatalytic reactor has been observed for 10 cycles of treatment of imidacloprid bearing wastewater. The enhanced photocatalytic activity of UV light-exposed (20 min), superhydrophilic, nano-calcite @ PF for mineralization of pollutants suggests it to be an efficient solar photocatalyst for environmental applications.

Fabrication and characterization of novel, cost-effective graphitic carbon nitride/Fe coated textile nanocomposites for effective degradation of dyes and biohazards.

Textile-based photocatalysts are the new materials that can be utilized as an effective sustainable solution for biochemical hazards. Hence, we aimed to develop a sustainable, cost-effective, and facile approach for the fabrication of photocatalytic fabric using graphitic carbon nitride (g-C3N4) and ferric-based multifunctional nanocomposite. Bulk g-C3N4 was prepared from urea by heating it at 500 °C for 2 h. The structure of ball-milled g-C3N4 was engineered by doping with various amounts of iron (III) chloride hexahydrate solution (0.006 mol/L) and sintered at 90 °C for 24 h to prepare g-C3N4-nanosheets/α-Fe2O3 composites. These nanocomposites have potential avenues towards rational designing of g-C3N4 for improved photocatalytic, antibacterial, and antiviral behavior. The prepared nanocomposite was characterized for its surface morphology, chemical composition, crystal structure, catalytic, antibacterial, and antiviral behavior. The fabrication of ferric doped g-C3N4 nanocomposites was characterized by SEM, EDX, FTIR, and XRD analysis. The coated fabric nanocomposite was characterized for methylene blue dye degradation under visible light, antibacterial and antiviral behavior. The developed textile-based photocatalyst has been found with very good recyclability with photocatalytic degradation of dye up to 99.9 % when compared to conventional g-C3N4 powder-based photocatalyst.

Enhanced Solar Photocatalytic Activity of Thermally Stable I:ZnO/Glass Beads for Reduction of Cr(VI) in Tannery Effluent.

Chromium (VI) in tannery effluent is one of the major environmental concerns for the environmentalists due to the hazardous nature of Cr(VI) ions. To reduce Cr(VI) to Cr(III) as an innocuous moiety, pure and I-doped ZnO was grafted over the etched surface of glass beads by successive ionic layer adsorption and reaction (SILAR). Powdered, pure, and I-doped ZnO scrapped from the surface of glass beads was characterized for crystallinity, morphology, and elemental composition by XRD, SEM, TEM, and EDX. The optical properties of both photocatalysts revealed that owing to optimized iodine doping of ZnO, reduction in the bandgap was observed from 3.3 to 2.9 eV. The crystalline nano-bricks of I:ZnO adhered to glass beads were investigated to have remarkable capability to harvest sunlight in comparison to intrinsic ZnO nanodiscs. The thermal stability of I:ZnO was also found to be much improved due to doping of ZnO. The photocatalytic activities of ZnO/GB and I:ZnO/GB were compared by extent of reduction of Cr(VI) under direct natural sunlight (600-650 KWh/m2). The disappearance of absorbance peaks associated with Cr(VI) after treatment with I:ZnO/GB confirmed higher photocatalytic activity of I:ZnO/GB. The reaction parameters of solar photocatalytic reduction, i.e., initial pH (5-9), initial concentration of Cr(VI) (10-50 ppm), and solar irradiation time (1-5 h) were optimized using response surface methodology. The solar photocatalytic reduction of Cr(VI) to Cr(III) present in real tannery effluent was examined to be 87 and 98%, respectively, by employing ZnO/GB and I:ZnO/GB as solar photocatalysts. The extent of reduction was also confirmed by complexation of Cr(VI) and Cr(III) present in treated and untreated tannery waste with 1, 5-diphenylcarbazide. The results of AAS and UV/vis spectroscopy for the decrease in concentration of Cr also supported the evidence of higher efficiency of I:ZnO/GB for reduction of Cr(VI) in tannery effluent. Reusability of the fabricated photocatalyst was assessed for eight cycles, and magnificent extent of reduction of Cr(VI) indicated its high efficiency. Conclusively, I:ZnO/GB is a potential and cost-effective candidate for Cr(VI) reduction in tannery effluent under natural sunlight.

Synthesis of Functionalized Carboxylated Graphene Oxide for the Remediation of Pb and Cr Contaminated Water.

With the growing scarcity of water, the remediation of water polluted with heavy metals is the need of hour. The present research work is aimed to address this problem by adsorbing heavy metals ions (Pb (II) and Cr (VI)) on modified graphene oxide having an excess of carboxylic acid groups. For this, graphene oxide (GO) was modified with chloroacetic acid to produce carboxylated graphene oxide (GO-COOH). The successful synthesis of graphene oxide and its modification has been confirmed using Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray Diffraction (XRD), Scanning electron microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and Transmission electron microscopy (TEM). The increase in surface area of graphene oxide after treatment with chloroacetic acid characterized by BET indicated its successful modification. A batch experiment was conducted to optimize the different factors affecting adsorption of both heavy metals on GO-COOH. After functionalization, we achieved maximum adsorption capacities of 588.23 mg g-1 and 370.37 mg g-1 for Pb and Cr, respectively, by GO-COOH which were high compared to the previously reported adsorbents of this kind. The Langmuir model (R2 = 0.998) and Pseudo-second-order kinetic model (R2 = 0.999) confirmed the monolayer adsorption of Pb and Cr on GO-COOH and the chemisorption as the dominant process governing adsorption mechanism. The present work shows that the carboxylation of GO can enhance its adsorption capacity efficiently and may be applicable for the treatment of wastewater.

Impact of foliar application of syringic acid on tomato (Solanum lycopersicum L.) under heavy metal stress-insights into nutrient uptake, redox homeostasis, oxidative stress, and antioxidant defense.

Soil contamination with toxic heavy metals [such as lead (Pb)] is becoming a serious global problem due to the rapid development of the social economy. However, accumulation of Pb in plant parts is very toxic for plant growth and decreases crop yield and productivity. In the present study, we have investigated the different concentrations of Pb in the soil i.e., [0 (no Pb), 50, and 100 mg kg-1] to study plant growth and biomass, photosynthetic pigments and gas exchange characteristics, oxidative stress indicators and the response of various antioxidants (enzymatic and non-enzymatic), nutritional status of the plant, organic acid exudation pattern and also Pb accumulation in the roots and shoots of the plants of two varieties of tomato (Solanum lycopersicum L.) i.e., Roma and Cchuas, grown under different levels of synergic acid [no spray (NS), water spray (WS), 0.3-0.5°µM]. Results from the present study showed that the increasing levels of Pb in the soil decreased non-significantly (P < 0.05) shoot length, root length, shoot fresh weight, root fresh weight, shoot dry weight, root dry weight, chlorophyll-a, chlorophyll-b, total chlorophyll, carotenoid content, net photosynthesis, stomatal conductance, transpiration rate, soluble sugar, reducing sugar, non-reducing sugar contents, calcium (Ca2+), magnesium (Mg2+), iron (Fe2+), and phosphorus (P) contents in the roots and shoots of the plants. However, Pb toxicity also induced oxidative stress in the roots and shoots of the plants by increasing malondialdehyde (MDA), hydrogen peroxide (H2O2), and electrolyte leakage (EL) which also induced increased the compounds of various enzymatic and non-enzymatic antioxidants and also organic acids exudation pattern in the roots such as fumaric acid, acetic acid, citric acid, formic acid, malic acid, oxalic acid contents and increased the concentration of Pb in different parts of the plants. Results also show that the Cchuas showed better growth and development compared to Roma, under the same levels of Pb in the soil. The alleviation of Pb toxicity was induced by the application of synergic acid, and results showed that the application of synergic acid increased plant growth and biomass and also increased the gas exchange characteristics and antioxidant capacity in the roots and shoots of the plants. Research findings, therefore, suggested that synergic acid application can ameliorate Pb toxicity in S. lycopersicum varieties and result in improved plant growth and composition under metal stress as depicted by balanced exudation of organic acids.

Alleviation of Chlorpyrifos Toxicity in Maize (Zea mays L.) by Reducing Its Uptake and Oxidative Stress in Response to Soil-Applied Compost and Biochar Amendments.

Chlorpyrifos (CP) is a pesticide used extensively in agricultural crops. Residual CP has been found in a variety of soils, vegetables and fruits indicating a serious danger to humans. Therefore, it is necessary to restrict its entry into agricultural products for food safety. A wire-house pot experiment was conducted with maize plants in biochar- and compost-amended soil (at 0.25% and 0.50%, respectively, in weight-by-weight composition) contaminated with 100 and 200 mg kg-1 of CP, respectively. Results indicated toxicity at both CP levels (with 84% growth reduction) at CP 200 mg kg-1. However, application of compost and biochar at the 0.50% level improved the fresh weight (2.8- and 4-fold, respectively). Stimulated superoxide dismutase (SOD) and peroxidase (POX) activities and depressed catalase (CAT) activity were recorded in response to CP contamination and were significantly recovered by the amendments. Both amendments significantly decreased the CP phytoavailability. With biochar, 91% and 76% reduction in the CP concentration in maize shoots and with compost 72% and 68% reduction was recorded, at a 0.50% level in 100 and 200 mg kg-1 contaminated treatments respectively. Compost accelerated the CP degradation in postharvest soil. Therefore, biochar and compost amendments can effectively be used to decrease CP entry in agricultural produce by reducing its phytoavailability.

Chemical fractionation and risk assessment of trace elements in sewage sludge generated from various states of Pakistan.

In the developing world, rapid urbanization and industrialization produces an enormous volume of wastes daily. This study was aimed to explore the potential and risks associated with sewage sludge through the characterization and fractionation technique. Sewage sludge samples were collected from various wastewater treatment in five different cities of Pakistan. Considerable amounts of macro-elements were detected in all types of sewage sludge samples. The pHw of all sewage sludge were neutral to slightly alkaline in reaction. Total organic carbon (TOC) was maximum (18.73%) with Coca-Cola sewage sludge (CSS) while the minimum (14.69%) was with Water and Sanitation Agency (WASA) sewage sludge (WSS). Percent relative distribution of cadmium (Cd) was higher in residual fraction (F4) up to 52% in the Nestle wastewater treatment plant, Sheikhupura (NSS). The chromium (Cr) concentration in Kasur sewage sludge (KSS) was extremely in mobile fraction (exchangeable) as compared with all other sludge samples, therefore showing a higher level of risk assessment code. While in the case of Iron (Fe), mobility was less and its maximum portion was noted in residual fraction (F4) of all sewage sludge samples. Percent distribution of manganese (Mn) showed variable trends for different sewage sludge samples. Zinc (Zn) concentration showed high mobility (exchangeable fraction) in case of NUST wastewater treatment plant, Islamabad (NTS) (31.16%) and WSS (37.83%) as compared with other sewage sludges. The risk assessment code indicated that Zn and Ni had a medium level of risk with I-9 Sector wastewater treatment plant, Islamabad (ISS), CSS, KSS, and NSS whereas these pose a high risk with NTS and WSS. Based on physicochemical properties, nutrients, trace elements, mobility, and risk assessment code, it was concluded that KSS should not be recommended at any application rate while NTS and WSS may be used at low application rates whereas ISS, CSS, and NSS may be used for agricultural crop production.