A novel and sustainable composite of L@PSAC for superior removal of pharmaceuticals from different water matrices: Production, characterization, and application.

This study endeavors to develop cost-effective environmentally friendly technology for removing harmful residual pharmaceuticals from water and wastewater by utilizing the effective adsorption of pistachio shell (PS) biochar and the degradation potency of laccase immobilized on the biochar (L@PSAC). The carbonatization and activation of the shells were optimized regarding temperature, time, and NH4NO3/PS ratio. This step yielded an optimum PS biochar (PSAC) with the highest porosity and surface area treated at 700 °C for 3 h using an NH4NO3/PS ratio of 3% wt. The immobilization of laccase onto PSAC (L@PSAC) was at its best level at pH 5, 60 U/g, and 30 °C. The optimum L@PSAC maintained a high level of enzyme activity over two months. Almost a complete removal (>99%) of diclofenac, carbamazepine, and ciprofloxacin in Milli-Q (MQ) water and wastewater was achieved. Adsorption was responsible for >80% of the removal and the rest was facilitated by laccase degradation. L@PSAC maintained effective removal of pharmaceuticals of ≥60% for up to six treatment cycles underscoring the promising application of this material for wastewater treatment. These results indicate that activated carbon derived from the pistachio shell could potentially be utilized as a carrier and adsorbent to efficiently remove pharmaceutical compounds. This enzymatic physical elimination approach has the potential to be used on a large-scale.

Novel chitosan/citric acid modified pistachio shell/halloysite nanotubes cross-linked by glutaraldehyde biocomposite beads applied to methylene blue removal.

In this study, Cht/PS-CA/HNT biocomposite adsorbent was synthesized using halloysite nanotube as nanomaterial, chitosan which is a biodegradable and biocompatible biopolymer, pistachio shell as biomass source, citric acid as biomass modifier. The removal of methylene blue dyestuff on the synthesized new Cht/PS-CA/HNT from the aqueous medium by adsorption method was investigated. Experimental parameters such as dye concentration, contact time, amount of adsorbent, solution pH and temperature, which affect the adsorption process, were investigated. The adsorption experimental data were analyzed with the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherms, which are widely used in aqueous solutions, and it was decided that Langmuir is the most suitable isotherm. The maximum adsorption capacity of the monolayer was calculated to be 111.14 mg/g. Optimum contact time and adsorbent dose were determined as 90 min and 1 g/L. Adsorption experimental data were applied for Pseudo-first-order and Pseudo-second-order kinetic models and it was decided that the most suitable kinetic model was pseudo-second-order. Thermodynamic evaluation of adsorption showed that adsorption is endothermic and adsorption is spontaneous.

In the present study, it was determined that chitosan beads prepared using citric acid modified pistachio shells and HNT have strong adsorption properties for dyestuff removal, which is one of the important causes of environmental pollution. The novelty of this work is based on the development of a new composite adsorbent that can be synthesized in a simple and fast method and does not require expensive reagents or complex equipment. Another innovation is that MB dyestuff, which has a highly harmful effect, can be easily removed from polluted water by using simple biowaste-based adsorbents by adopting appropriate procedures.

Development and characterization of gelatin-based biodegradable films incorporated with pistachio shell hemicellulose.

This study aimed to incorporate pistachio shell hemicellulose into a film of gelatin and glycerol for the production of biodegradable films. The gelatin and glycerol are chosen because of their functional properties, which make it extensively used in food industry. The film composition was defined after a statistical optimization by central composite face-centered design and response surface methodology. The hemicellulose/gelatin ratio of 35.93% and the glycerol ratio of 18.02% were the optimum conditions to obtain lower film water solubility, higher tensile strength, and elongation at break values. The physical, structural, mechanical, and barrier properties of the developed hemicellulose-gelatin film were analyzed and compared with those of the gelatin film. Tensile strength and film water solubility values were reduced significantly with hemicellulose incorporation from 20.41 to 16.64 MPa and 49.57 to 39.21%, respectively, while EB was enhanced by 4.34 times. In addition, hemicellulose incorporation enhanced the water vapor permeability and the film degradation in the soil. The films were also examined by Fourier transform infrared spectroscopy and differential scanning calorimetry. The novelty of this study is to use pistcahio shell hemicellulose in the production of an edible film for the first time. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-024-05968-4.

Evaluation of Thermal Properties of Composites Prepared from Pistachio Shell Particles Treated Chemically and Polypropylene.

The purpose of the present work was to prepare polypropylene (PP) matrix composited filled with chemically treated pistachio shell particles (PTx), and evaluate their effect on the composites' thermal properties. PP-PTx composites were formulated in different PTx content (from 2 to 10 phr) in a mixing chamber, using the melt-mixing process. The PTx were chemically treated using a NaOH solution and infrared spectroscopy (FTIR). According to thermogravimetric analysis (TGA), the treatment of pistachio shell particles resulted in the remotion of lignin and hemicellulose. The thermal stability was evaluated by means of TGA, where the presence of PTx in composites showed a positive effect compared with PP pristine. Thermal properties such as crystallization temperature (Tc), crystallization enthalpy (∆Hc), melting temperature (Tm) and crystallinity were determinate by means differential scanning calorimetry (DSC); these results suggest that the PTx had a nucleation effect on the PP matrix, increasing their crystallinity. Dynamic mechanical analysis (DMA) showed that stiffness of the composites increase compared with that PP pristine, as well as the storage modulus, and the best results were found at a PTx concentration of 4 phr. At higher concentrations, the positive effect decreased; however, they were better than the reference PP.

In situ green synthesis of highly fluorescent Fe2 O3 @CQD/graphene oxide using hard pistachio shells via the hydrothermal-assisted ball milling method.

In this study, highly photoluminescent and photocatalytic Fe2 O3 @carbon quantum dots/graphene oxide nanostructures were synthesized using ball milling-assisted hydrothermal synthesis with hard pistachio shells. Different analyses, such as X-ray diffraction, energy dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy were used to study the product structure. Scanning electron microscopy and transmission electron microscopy images were used to study product size and morphology. Optical properties of the as-synthesized nanomaterials were investigated using ultraviolet-visible light and photoluminescence analyses. To increase photoluminescence intensity, ethylene diamine tetraacetic acid, polyethylene glycol, polyvinylpyrrolidone, and acetylacetonate anions were used to modify the product surface. Thermal stability of the product was studied using thermal gravimetric analysis. Finally, photocatalytic activity and surface adsorption of the product were investigated; the produce was found to be highly photoluminescent with high photocatalytic and surface activities.

Development of Ultra-Performance Liquid Chromatography-Mass Spectrometry Method for Simultaneous Determination of Three Cationic Dyes in Environmental Samples.

Lower dye concentrations and the presence of several dyes along with other matrices in environmental samples restrict their determination. Herein, a highly sensitive and rapid ultra-performance tandem mass spectrometric method was developed for simultaneous determination of cationic dyes, namely methylene blue (MB), rhodamine B (RB) and crystal violet (CV), in environmental samples. To preconcentrate environmental samples, solid-phase extraction cartridges were developed by using hydrogen peroxide modified pistachio shell biomass (MPSB). The surface morphological and chemical functionalities of MPSB were well characterized. The developed method was validated considering different validation parameters. In terms of accuracy and precision, the %RSD for all three dyes at all four concentration points was found to be between 1.26 and 2.76, while the accuracy reported in terms of the recovery was found to be 98.02%-101.70%. The recovery was found to be in the range of 98.11% to 99.55%. The real sample analysis shows that MB, RB, and CV were found in the ranges of 0.39-5.56, 0.32-1.92 and 0.27-4.36 µg/mL, respectively.

Enhanced production, one-step affinity purification, and characterization of laccase from solid-state culture of Lentinus tigrinus and delignification of pistachio shell by free and immobilized enzyme.

Laccase mediated bio-delignification has shown promising results for the removal of lignin from bio-wastes and for providing a sustainable future for using of lignocellulosic materials in different industries. This study reports an extracellular laccase from Lentinus tigrinus with delignification capability. The production of laccase was enhanced through a solid-state fermentation on the pistachio shell bio-waste to 172.0 U mg-1 (8.2-fold) by one-factor-at-a-time optimizing of fermentation conditions. Laccase was purified using a new synthetic affinity resin yielding a specific activity of 543.6 U mg-1 and a 23.9-fold purification. The purified laccase was then immobilized covalently on the large pore magnetic SBA-15. Compared to free enzyme, immobilized enzyme maintained more stable at pH 2.0-11.0 and 25-55 °C, and against organic solvents, surfactants, metal ions, and inhibitors. The activity of both forms of the enzyme was increased with Cu2+, Ca+2, cetyltrimethylammonium bromide, and ethyl acetate. A 0.72 V redox potential caused enzyme specificity to various substrates. 80% of lignin content of the bio-waste was removed by 50 U mL-1 of immobilized enzyme after 8 h fermentation and delignification efficiency was greatly increased by applying higher enzyme dosages, surfactants, and organic solvents. In addition, residual activity was more than 50% after 20 cycles of delignification. The results of delignification were confirmed by GC-MS, SEM, and composition analysis of pistachio shells. This study illustrated the notable promise of the enzyme for biotechnological and environmental applications.

Determination of energy values in pistachio shell powder and soybean hulls fed to gestating and lactating sows.

Pistachio shell powder is a high-fiber co-product from the pistachio nut industry that may provide energy and nutrients in animal diets, but no data have been reported for the nutritional value of pistachio shell powder when fed to pigs. Two experiments were, therefore, conducted to test the hypothesis that apparent total tract digestibility (ATTD) of gross energy (GE), dry matter (DM), and total dietary fiber (TDF) and concentration of digestible energy (DE) in pistachio shell powder are not different from those in soybean hulls when fed to gestating or lactating sows. In experiment 1, 24 gestating sows were housed in metabolism crates and fed a corn-based basal diet or 2 diets that contained corn and 20% pistachio shell powder or corn and 20% soybean hulls. Sows were fed experimental diets for 13 d with feces and urine being quantitatively collected for 4 d after 6 d of adaptation. In experiment 2, 24 lactating sows were housed in farrowing crates and fed a diet based on corn and soybean meal (SBM) or 2 diets that contained corn, SBM, and 20% of either pistachio shell powder or soybean hulls, and feces were collected for 6 d after 7 d of adaptation to the diets. Results indicated that for gestating sows, the diet containing soybean hulls had greater (P < 0.05) ATTD of DM, GE, and TDF than the diet containing pistachio shell powder. The DE and metabolizable energy (ME) in the pistachio shell powder diet were less (P < 0.05) than in the basal diet and the diet containing soybean hulls. The ME in pistachio shells (2,606 kcal/kg DM) was less (P < 0.05) than in soybean hulls (3,645 kcal/kg DM). When fed to lactating sows, ATTD of DM, GE, and TDF in the diet containing pistachio shell powder was less (P < 0.05) than in the diet containing soybean hulls or in the basal diet. The DE in the diet containing pistachio shell powder was also less (P < 0.05) than in the soybean hulls diet. The DE in pistachio shell powder (1,664 kcal/kg DM) was less (P < 0.05) than in soybean hulls (2,795 kcal/kg DM). In conclusion, the ATTD of DM and GE and the DE in pistachio shell powder were less than in soybean hulls, and inclusion in lactation diets, therefore, needs to be limited.

Effect of pistachio shell as a carbon source to regulate C/N on simultaneous removal of nitrogen and phosphorus from wastewater.

Acid-pretreated pistachio shells were used as carbon sources to investigate the effects of carbon source dosage on simultaneous nitrogen and phosphorus removal under different carbon/nitrogen (C/N) ratios (7, 9, and 11). Results showed that C/N was positively correlated with mixed liquor suspended solids (MLSS) (R2 = 0.998, p < 0.01) and f value (R2 = 0.975, p < 0.05). Moreover, it was negatively correlated with the sludge volume index (SVI) (R2 =  - 0.959, p < 0.05). C/N was also significantly negatively related to chemical oxygen demand removal rate (R2 =  - 0.986, p < 0.05) and positively related to ammonia nitrogen (NH4+-N), total nitrogen (TN), and total phosphorus (TP) removal rate (p < 0.05), the correlation coefficients were 0.992, 0.990 and 0.994, respectively. In the reactor with C/N of 11, the MLSS concentration and f value were the highest, the SVI was the lowest, and the removal efficiencies of NH4+-N (85.49 % ± 1.96 %), TN (84.19 % ± 1.42 %) and TP (94.10 % ± 1.67 %) were the highest. Furthermore, the relative abundance of denitrifying bacteria was the highest in the reactor. The abundance of nitrifying bacteria and phosphorus-removal bacteria was also relatively high.

Alkylation modified pistachio shell-based biochar to promote the adsorption of VOCs in high humidity environment.

The objective of this work was to evaluate the adsorption capacity of alkylated modified porous biochar prepared by esterification and etherification (PSAC-2) for low concentrate volatile organic compounds (VOCs, toluene and ethyl acetate) in high humidity environment by experiments and theoretical calculations. Results showed that PSAC-2 has a large specific surface area and weak surface polarity, at 80% relative humidity, its capacities for toluene and ethyl acetate adsorption could be maintained at 92% and 87% of the initial capacities (169.9 mg/g and 96.77 mg/g). The adsorption behaviors of toluene, ethyl acetate, and water vapor were studied by adsorption isotherms, and isosteric heat was obtained. The desorption activation energy was obtained by temperature programmed desorption experiment. The outcomes manifested that the PSAC-2 can achieve strong adsorption performance for weakly polar molecules. Through density functional theory (DFT) simulations, owing to the interaction of hydrogen bonds, oxygen-containing groups became a significant factor influencing the adsorption of VOCs in humid environments. These results could provide an important reference for VOCs control in a high humidity environment.

Eco-friendly approach for efficient catalytic degradation of organic dyes through peroxymonosulfate activated with pistachio shell-derived biochar and activated carbon.

This study introduces a simple method for the preparation of biochar (BCP) and activated carbon using pistachio (ACP) external hull as residual solid waste. Low-cost raw materials, biodegradable, recyclable and organic solid wastes are advantages of this method. Furthermore, complete degradation of methyl orange (MO) and methylene blue (MB) to H2O and CO2 as eco-friendly compounds in mild reaction condition occurs at a short time. Also, the effects of crucial parameters (temperature, time, catalyst dosage, initial dye and oxidant concentration, initial reaction pH level and radical scavengers), capability, adaptability, performance and reusability of ACP were also evaluated. The results displayed that dyes could be decomposed effectively by the PMS/ACP-800 system. Furthermore, the sulphate radical (SO4∙-) was a major active role in the degradation process, while hydroxyl radical (•OH) played a minor role. Overall, ACP had yielded high degradation of MB and MO dyes; therefore, ACP-800 could be effectively and reliably applied in the treatment of industry effluents containing MB and MO dyes.

Iron-modified activated carbon derived from agro-waste for enhanced dye removal from aqueous solutions.

BACKGROUND AND AIM: Finding a cost-effective adsorbent can be an obstacle to large-scale applications of adsorption. This study used an efficient activated carbon adsorbent based on agro-waste for dye removal. METHODS: Pistachio shells as abundant local agro-wastes were used to prepare activated carbon. Then, it was modified with iron to improve its characteristics. Acid red 14 was used as a model dye in various conditions of adsorption (AR14 concentration 20-150 mg L-1, pH 3-10, adsorbent dosage 0.1-0.3 g L-1, and contact time 5-60 min). RESULTS: A mesoporous adsorbent was prepared from pistachio shells with 811.57 m2 g-1 surface area and 0.654 cm3 g-1 pore volume. Iron modification enhanced the characteristics of activated carbon (surface area by 33.3% and pore volume by 64.1%). Adsorption experiments showed the high effectiveness of iron-modified activated carbon for AR14 removal (>99%, >516 mg g-1). The adsorption followed the pseudo-second kinetic model (k = 0.0005 g mg-1 min-1) and the Freundlich isotherm model (Kf = 152.87, n = 4.61). Besides, the reaction occurred spontaneously (ΔG0 = -36.65 to -41.12 kJ mol-1) and was exothermic (ΔH0 = -41.86 kJ mol-1 and ΔS0 = -3.34 J mol-1 K-1). CONCLUSION: Iron-modified activated carbon derived from pistachio shells could be cost-effective for the treatment of industrial wastewater containing dyes.

Mathematical modeling and experimental study of VOC adsorption by Pistachio shell-based activated carbon.

The adsorption of benzene vapor, as a volatile organic component, from inert gas (N2) by activated carbon was studied experimentally in the isothermal fixed bed reactor at various operating conditions. The activated carbon used in this study had pistachio shell base with high surface area. To improve the adsorption capacity of VOC vapor, the activated carbon was chemically treated with H2SO4, HNO3, NaOH, and NH3 solutions. The saturated adsorption capacities of benzene on initial activated carbon and treated samples were measured and compared. The results showed that the activated carbon treated with nitric acid had higher adsorption capacity than others samples, 640 mg/g. In addition, a mathematical model for adsorption in a fixed bed reactor was proposed in this study. The model results had good agreement with experimental data. In order to demonstrate the effects of operating conditions on adsorption and breakthrough curve, the experimental tests and simulation runs were carried out at various gas flow rate, temperature, and benzene concentration. The results showed that with increase VOC concentration from 700 to 1000 ppm, the total time of adsorption was decreased from 25 to 21 h and breakthrough point appeared earlier.

Pistachio Shell-Derived Carbon Activated with Phosphoric Acid: A More Efficient Procedure to Improve the Performance of Li-S Batteries.

A sustainable and low-cost lithium-sulfur (Li-S) battery was produced by reusing abundant waste from biomass as a raw material. Pistachio shell was the by-product from the agri-food industry chosen to obtain activated carbon with excellent textural properties, which acts as a conductive matrix for sulfur. Pistachio shell-derived carbon activated with phosphoric acid exhibits a high surface area (1345 m2·g-1) and pore volume (0.67 cm3·g-1), together with an interconnected system of micropores and mesopores that is capable of accommodating significant amounts of S and enhancing the charge carrier mobility of the electrochemical reaction. Moreover, preparation of the S composite was carried out by simple wet grinding of the components, eliminating the usual stage of S melting. The cell performance was very satisfactory, both in long-term cycling measurements and in rate capability tests. After the initial cycles required for cell stabilization, it maintained good capacity retention for the 300 cycles measured (the capacity loss was barely 0.85 mAh·g-1 per cycle). In the rate capability test, the capacity released was around 650 mAh·g-1 at 1C, a higher value than that supplied by other activated carbons from nut wastes.

Potential of pistachio shell biochar and dicalcium phosphate combination to reduce Pb speciation in spinach, improved soil enzymatic activities, plant nutritional quality, and antioxidant defense system.

Lead-contaminated soils are becoming an ecological risk to the environment because of producing low-quality food which is directly causing critical health issues in humans and animals. We hypothesized that incorporation of dicalcium phosphate (DCP), eggshell powder (ESP) and biochar (BH) at diverse rates into a Pb-affected soil can proficiently immobilize Pb and decline its bioavailability to spinach (Spinacia oleracea L.). A soil was artificially spiked with Pb concentration (at 600 mg kg-1) and further amended with DCP, ESP, and BH (as sole treatments at 2% and in concoctions at 1% each) for immobilization of Pb in the soil. The interlinked effects of applied treatments on Pb concentrations in shoots and roots, biomass, antioxidants, biochemistry, and nutrition of spinach were also investigated. Results depicted that the highest reduction in DTPA-extractable Pb and the concentrations of Pb in shoots and roots was achieved in DCP1%+BH1% treatment that was up to 58%, 66%, and 53%, respectively over control. Likewise, the DCP1%+BH1% treatment also showed the maximum shoot and root dry weight (DW), chlorophyll-a (Chl-a) and chlorophyll-b (Chl-b) contents and relative water content (RWC) in spinach up to 92%, 121%, 60%, 65%, and 30%, respectively, compared to control. Likewise, DCP1%+BH1% treatment noticeably improved antioxidant enzymes, biochemistry, and nutrition in the leaves. Moreover, the DCP1%+BH1% treatment depicted mostly enhanced activities of dehydrogenase, catalase, acid phosphatase, alkaline phosphatase, phosphomonoesterase, urease, protease and B-glucosidase in the post-harvested soil up to 118%, 345%, 55%, 92%, 288%, 107%, 53% and 252%, respectively over control.

Production of cellulose nanocrystals from pistachio shells and their application for stabilizing Pickering emulsions.

This study presents isolation and characterization of cellulose nanocrystals (CNC) from pistachio shell and their application to stabilize Pickering emulsion. Pistachio shell (PS) is an agro-waste with an attractive source of cellulose. Alkali and bleaching treatments were performed for removing hemicellulose and lignin and purification of cellulose, while cellulose nanocrystals were obtained by acid hydrolysis. Hydrolysis using H2SO4 was very severe that led to formation of amorphous structures. While, hydrolysis reaction by HCl for 180min in concentration of 3M was recognized as the best conditions to extract CNCs with yield of 77.1% and crystallinity of 79.4%. FE-SEM images represented both rod-like and spherical shapes of CNC and TEM image showed particles with mean diameter of 68.8±20.7nm. Chemical structure and thermal properties of CNC were characterized by FTIR and TGA analysis. In order to evaluate emulsifier ability of CNCs, different concentrations of CNCs were dispersed in an oil in water emulsions as the Pickering agent. By increasing the CNC concentration, stability of emulsions against heating, stresses and storage time enhanced while the mean diameter of oil droplets decreased. The results of this study indicated high potential of CNCs as an environmental friendly material for food emulsion preparation.

Combustion of pistachio shell: physicochemical characterization and evaluation of kinetic parameters.

The study of different renewable energy sources has been intensifying due to the current climate changes; therefore, the present work had the objective to characterize physicochemically the pistachio shell waste and evaluate kinetic parameters of its combustion. The pistachio shell was characterized through proximate analysis, ultimate analysis, SEM, and FTIR. The thermal and kinetic behaviors were evaluated by a thermogravimetric analyzer under oxidant atmosphere between room temperature and 1000 °C, in which the process was performed in three different heating rates (20, 30, and 40 °C min-1). The combustion of the pistachio shell presented two regions in the derivative thermogravimetric curves, where the first represents the devolatilization of volatile matter compounds and the second one is associated to the biochar oxidation. These zones were considered for the evaluation of the kinetic parameters E a , A, and f(α) by the modified method of Coats-Redfern, compensation effect, and master plot, respectively. The kinetic parameters for zone 1 were E a1 = 84.11 kJ mol-1, A 1 = 6.39 × 106 min-1, and f(α)1 = 3(1 - α)2/3, while for zone 2, the kinetic parameters were E a2 = 37.47 kJ mol-1, A 2 = 57.14 min-1, and f(α)2 = 2(1 - α)1/2.