Search Results (176)

The objective of this study is to assess the efficacy of walnut shell-derived activated carbon with phosphoric acid (WSAC) in the removal of ciprofloxacin (CIP), diclofenac (DC), and sulfamethoxazole (SMX) from aqueous solutions and real wastewater. WSAC was characterized using various analytical techniques such as specific surface area and pore size distribution determination, elemental analysis, SEM images, and FT-IR spectroscopy. The BET-specific surface area of WSAC was determined to be 1428 m² g⁻¹. The surface is characterized by the presence of irregular pits of varying dimensions and shapes. The adsorption of SMX, CIP, and DC from aqueous solutions using WSAC was tested under various parameters, including contact time, adsorbent dosage, initial concentration, pH, and temperature. The adsorption of SMX, CIP, and DC was found to be in accordance with the Langmuir isotherm model, which suggests that monomolecular adsorption is the predominant mechanism. The maximum adsorption capacities of WSAC towards SMX, CIP, and DC were calculated to be 476.2, 185.2, and 135.1 mg g⁻¹, respectively. The adsorption of SMX, CIP, and DC were found to be consistent with the pseudo-second-order model. Thermodynamic analyses demonstrated the spontaneous and endothermic nature of SMX, CIP, and DC adsorption onto WSAC. The adsorption performances of SMX, CIP, and DC on WSAC were found to be 60.2%, 77.4%, and 74.2%, respectively in the effluent from the municipal wastewater treatment plant. In conclusion, WSAC may be regarded as a readily available, eco-friendly, and efficient substance for the extraction of SMX, CIP, and DC from wastewater and aqueous solutions. Full article

Walnuts possess significant nutritional and economic value. Fast and accurate sorting of shells and kernels will enhance the efficiency of automated production. Therefore, we propose a FastQAFPN-YOLOv8s object detection network to achieve rapid and precise detection of unsorted materials. The method uses lightweight Pconv (Partial Convolution) operators to build the FasterNextBlock structure, which serves as the backbone feature extractor for the Fasternet feature extraction network. The ECIoU loss function, combining EIoU (Efficient-IoU) and CIoU (Complete-IoU), speeds up the adjustment of the prediction frame and the network regression. In the Neck section of the network, the QAFPN feature fusion extraction network is proposed to replace the PAN-FPN (Path Aggregation Network—Feature Pyramid Network) in YOLOv8s with a Rep-PAN structure based on the QARepNext reparameterization framework for feature fusion extraction to strike a balance between network performance and inference speed. To validate the method, we built a three-axis mobile sorting device and created a dataset of 3000 images of walnuts after shell removal for experiments. The results show that the improved network contains 6071008 parameters, a training time of 2.49 h, a model size of 12.3 MB, an mAP (Mean Average Precision) of 94.5%, and a frame rate of 52.1 FPS. Compared with the original model, the number of parameters decreased by 45.5%, with training time reduced by 32.7%, the model size shrunk by 45.3%, and frame rate improved by 40.8%. However, some accuracy is sacrificed due to the lightweight design, resulting in a 1.2% decrease in mAP. The network reduces the model size by 59.7 MB and 23.9 MB compared to YOLOv7 and YOLOv6, respectively, and improves the frame rate by 15.67 fps and 22.55 fps, respectively. The average confidence and mAP show minimal changes compared to YOLOv7 and improved by 4.2% and 2.4% compared to YOLOv6, respectively. The FastQAFPN-YOLOv8s detection method effectively reduces model size while maintaining recognition accuracy. Full article

Chloride ions readily react with organic matter and other ions, resulting in the formation of disinfection by-products (DBPs) that exhibit heightened levels of toxicity, carcinogenicity, and mutagenicity. This study creatively employed waste walnut shells as self-templates and low-cost magnesium bicarbonate as a rigid template to successfully synthesize multifunctional porous carbon derived from walnut shells. Employing a series of characterization techniques, it was ascertained that the porous carbon material (WSC/Mg) synthesized via the dual-template method exhibited a distinct layered microscopic surface structure, with a predominance of C and O elements on the surface. The material displayed a high degree of graphitization, significant specific surface area, and abundant oxygen-containing surface functional groups. The incorporation of magnesium bicarbonate as a hard template improved the structure of the walnut shell porous carbon, resulting in a significant enhancement in mass transfer efficiency for the target product on the adsorbent and a substantial improvement in removal efficiency. In comparison with walnut shell-derived carbon using only self-templating, WSC/Mg exhibited a 17.26-fold increase in adsorption capacity for 2,4-dichlorophenol. Furthermore, even after four adsorption–desorption cycles, WSC/Mg-12 maintained an adsorption efficiency above 90%. It is remarkable that WSC/Mg-12 demonstrated exceptional resistance to interference from natural organic matter and pH variations. Moreover, the adsorbed saturated WSC/Mg-12 effectively treated real coke wastewater, resulting in an 80% color removal rate, 20% COD removal rate, and 15% ammonia nitrogen removal rate. In conclusion, this study presents an innovative approach for cost-effective and versatile porous carbon materials with extensive applications in water environment purification and biomass utilization. Full article

This study investigated the phytotoxicity of agro-industrial wastes (almond, walnut, pistachio and peanut shells, asparagus spears, and brewer’s spent grain) and their biochar through germination bioassays in several horticultural species: green pea, lettuce, radish, and arugula. Biowaste was pyrolyzed under controlled conditions to produce biochar, and both biowaste and biochar were characterized. Germination bioassay was conducted using seeds exposed to different dilutions of aqueous extract of biowaste and their biochar (0, 50, and 100%). Germination percentage, seed vigor, germination index, and root and aerial lengths were evaluated. The results showed that the phytotoxicity of the biowaste was significantly different to that of its biochar. The biochar obtained demonstrated changing effects on germination and seedling growth. In particular, biochar extracts from spent brewers grains, walnut shells, and pistachio shells showed 5–14% increases in seed vigor and root and aerial length. Furthermore, the response of different species to both agro-industrial waste and biochar revealed species-specific sensitivity. Seeds of lettuce and arugula species were more sensitive to aqueous extracts than radish and green peas. This knowledge not only elucidates the behavior of agro-industrial waste-based biochar in the early stage of plant development but also provides valuable insights regarding phytotoxicity, seed sensitivity, and the variables involved in germination. Full article

Slurry shields rely on the formation of a compact filter cake to maintain excavation face stability and ensure construction safety. In strata with high permeability, significant slurry loss occurs, making filter cake formation and air tightness maintenance challenging. In this study, light organic walnut shell was selected as an additive coarse particle material for slurry. Slurries incorporating two types of coarse particles, sand and walnut shell, were prepared, and tests on slurry permeation and air tightness of the filter cake were conducted in three different strata. The results indicate that the addition of coarse particles effectively improves filter cake formation and air tightness in high-permeability strata. It is essential to use graded particles in highly permeable strata, with controlled maximum and minimum particle sizes. As the content of coarse particles increases, the air tightness of the filter cake initially increases and then decreases. Notably, the air tightness of filter cakes containing walnut shell is superior to those containing sand. Replacing sand with walnut shell as a slurry plugging material enhances filter cake quality in high-permeability strata. For highly permeable strata with a permeability coefficient greater than 1.0 × 10⁻³ m/s, an addition of 30 g/L to 40 g/L is recommended. Full article

UV filters and parabens, as ingredients of cosmetics, are commonly occurring water pollutants. In our work, nutshells were used as biosorbents in the developed analytical procedure for the determination of UV filters and parabens in water samples. The shells obtained from walnuts, hazelnuts, peanuts and pistachios were applied as biosorbents. The proposed analytical method can be used as a powerful alternative to other methods for the analysis of UV filters and parabens in water samples. A method of carrying out the sorption step and its parameters, i.e., the effect of time, pH, and salt addition, was developed. A method for the desorption of analytes was also developed, in which the type and volume of solvent, and the desorption time, were established. The recoveries were in the range of 59–117% for benzophenones and lower recoveries from 14 to 75% for parabens. The results showed that nutshells can be used as low-cost, efficient and eco-friendly biosorbents for the determination of parabens and UV filters in water samples. These materials can be used as a ‘greener’ replacement for the commercially available adsorbents for the extraction of cosmetic ingredients from the environment. Full article

Biostimulants are an important alternative to improve and promote higher efficiency in cropping systems. Although the biostimulant industry has been developing for several years, there are still areas of opportunity for new sources of biostimulants as well as new ecofriendly extraction techniques that allow for a circular economy and the reuse of waste. Lignin is a heteropolymer that constitutes about 40% of the plant cell wall. A great source of lignin is agrowastes, giving it added value. Recently, its use has been tested in agronomy as a carrier of nutrients and pesticides. Walnuts are produced on a large scale in Northern Mexico, and the shell represents between 15 and 40% of its total weight. However, to obtain this biopolymer, to date, non-environmentally friendly techniques have been used; for this reason, it is necessary to find extraction alternatives to make this proposal sustainable. In this work, the obtaining and characterization of lignin through mild extraction conditions from nutshells and its evaluation as a biostimulant on the growth of tomato seedlings are reported. Lignin was extracted by hydrolysis with a mixture of acetic acid and distilled water (65:35 v/v). The results showed that it was possible to obtain 15% (w/w) lignin using mild solvents, evidenced by thermogravimetric analysis (TGA), proton magnetic nuclear resonance (H-RMN), and infrared (IR). Subsequently, lignin solutions were prepared at different concentrations, 0, 10, 50, and 100 ppm, and applied via foliar weekly to tomato seedlings. A greater fresh weight of the stem was found with 10 and 50 ppm, and the height and the fresh biomass increased with the three concentrations (10, 50, and 100 ppm), concluding that lignin extracted from nutshells using mild conditions can act as a plant biostimulant. Full article

Percarbonate (SPC) as a promising substitute for liquid H₂O₂ has many advantages in the application of in situ chemical oxidation (ISCO). Developing efficient, cost effective and environmentally friendly catalysts for SPC activation plays the key role in promoting the development of SPC-based ISCO. Herein, the walnut shell biomass was combined with ferric nitrate for the catalytic synthesis of Fe₃C@biochar composite (Fe₃C@WSB), which demonstrated high efficiency in activating SPC for the removal of diclofenac (DCF). The Fe₃C showed average crystallite size of 32.6 nm and the composite Fe₃C@WSB demonstrated strong adsorptivity. The prepared Fe₃C@WSB could activate both SPC and H₂O₂ with high efficiency at ca. pH 3 with extremely low leaching of iron, while in a weak acidic condition, higher efficiency of DCF removal was obtained in the Fe₃C@WSB/SPC process than in the Fe₃C@WSB/H₂O₂ process. Moreover, the Fe₃C@WSB/SPC and Fe₃C@WSB/H₂O₂ processes did not show significant differences when supplied with varying amounts of catalyst or oxidant, but the Fe₃C@WSB/SPC process exhibited stronger capability in dealing with relatively highly concentrated DCF solution. Based on quenching experiments and electron spin resonance (ESR) analysis, heterogeneous activation of SPC was assumed as the dominant route for DCF degradation, and both the oxidation by radicals, including •OH, •O₂⁻ and CO₃^•−, combined with electron transfer pathway contributed to DCF degradation in the Fe₃C@WSB/SPC process. The cycling experiment results also revealed the stability of Fe₃C@WSB. This work may cast some light on the development of efficient catalysts for the activation of SPC. Full article

In northwest China, changes in cultivation patterns and the scarcity of preferred hosts have forced Helicoverpa armigera to feed on the marginal host walnut (Juglans regia). However, the mechanisms allowing this adaptation remain poorly understood. Here, we investigated the behavioral, physiological, and molecular mechanisms underlying the local adaptation of this pest to walnut fruits. The green husk and shell generally contained higher levels of phytochemicals than the kernel. Bioassays revealed that the phytochemical-rich green husk and shell were less preferred, reduced larval fitness and growth, and elevated the activity of detoxification enzymes compared to the nutrient-rich kernel, which were further supported by a larger number of upregulated detoxification genes in insects fed green husks or shells based on transcriptome sequencing. Together, these data suggest that P450 genes (LOC110371778) may be crucial to H. armigera adaptation to the phytochemicals of walnuts. Our findings provide significant insight into the adaptation of H. armigera to walnut, an alternative host of lower quality. Meanwhile, our study provides a theoretical basis for managing resistance to H. armigera larvae in walnut trees and is instrumental in developing comprehensive integrated pest management strategies for this pest in walnut orchards and other agricultural systems. Full article

One method of preparing sludge for management and use is solar drying. To intensify the drying process, natural lignocellulosic additives can be used to alter the structure of the sludge and accelerate water evaporation. Light, hard materials with low absorption capacity are best suited for this purpose, e.g., walnut shells, which are unused waste. The aim of the study was to determine the impact of the evaluation of walnut shells on the sludge drying process and to assess the impact of the drying process on the chemical, physical, and fuel properties of the additive. The moisture content, crushing strength, chemical composition, and physical and fuel properties of mixtures were determined. A small addition of walnut shells (25%) was found to accelerate the drying process even in winter and spring (up to 30 days) compared to sludge without additives. Walnut shells retain their chemical composition and strength despite unfavourable conditions and a chemically aggressive environment, indicating they may be reused. The mixture containing sewage sludge and walnut shells has a calorific value of 15.6 MJ/kg, which is similar to wood; it is also fully biodegradable and suitable as a fertiliser to improve soil structure, as it contains approx. 80–90% DM (including approx. 40% carbon, 3% nitrogen, and other elements, such as phosphorus and potassium.) Full article

Recently, the influence of the concept of environmental sustainability has increased, which includes environmentally friendly measures related to reducing the consumption of petrochemical fuels and converting post-production feedstocks into raw materials for the synthesis of polymeric materials, the addition of which would improve the performance of the final product. In this regard, the development of bio-based polyurethane foams can be carried out by, among other things, modifying polyurethane foams with vegetable or waste fillers. This paper investigates the possibility of using walnut shells (WS) and the mineral fillers vermiculite (V) and perlite (P) as a flame retardant to increase fire safety and thermal stability at higher temperatures. The effects of the fillers in amounts of 10 wt.% on selected properties of the polyurethane composites, such as rheological properties (dynamic viscosity and processing times), mechanical properties (compressive strength, flexural strength, and hardness), insulating properties (thermal conductivity), and flame retardant properties (e.g., ignition time, limiting oxygen index, and peak heat release) were investigated. It has been shown that polyurethane foams containing fillers have better performance properties compared to unmodified polyurethane foams. Full article

The separation of walnut kernels and shells has long been regarded as a bottleneck, limiting processing efficiency, product quality, and industry advancement. In response to the challenges of improving separation accuracy and the inadequacy of existing equipment for meeting industry demands, this paper proposes an innovative walnut shell–kernel separation device based on machine vision technology. An experimental system was constructed, and key parameters were optimized to enhance its performance. The device comprises five main modules: material conveyance, image acquisition, control module, sorting module, and frame. Differential separation technology is used to convert the walnut material group into a stable particle flow, addressing the issue of missed selections due to material blockages. An enhanced YOLOv8n algorithm improves small object detection and interference resistance, enabling accurate identification of walnut kernels. The Box–Behnken Design and Artificial Neural Network prediction model was used to determine the optimal operating parameters for the device. Experimental results showed that effective differential separation was achieved when the dual-stage conveyor system operated at speeds of 0.2 m/s and 1 m/s. The improved I-YOLOv8n algorithm reached an accuracy of 98.8%. Using the neural network model, the optimal operational parameters were determined: an air pressure of 0.72 MPa, a jetting component angle of 10.16°, and a sorting height of 105.12 cm. Under these conditions, the device achieved an actual cleaning rate of 93.56%, demonstrating outstanding separation performance. Compared to traditional separation methods, this device offers significant advantages in terms of efficiency, quality, and ease of operation, providing new technological pathways and support for the automation and intelligent transformation of the walnut processing industry. In the future, the device is expected to undergo further improvements to meet broader market demand and serve as a reference for the separation of other agricultural products. Full article

As a by-product of wastewater treatment, sewage sludge can be used for natural, agricultural, or energy purposes. One method of preparing sludge for management and use is solar drying. To intensify the drying process, natural additives can be used to alter the structure of the sludge and accelerate the evaporation of water. This research aimed to evaluate the influences of different organic additives in sewage sludge mixtures on the physicochemical and energy parameters of briquettes. This research was carried out without thermal boosting in a 4 × 2.5 × 2 m plastic tunnel. The tunnel was equipped with three drying stations and control and measuring equipment. In two test series, sludge additives in the form of straw and lignocellulosic materials, sawdust, bark, woodchips, and walnut shells, were used. Briquettes were made from the resulting mixtures and then subjected to physical and chemical analyses. This research showed high variability in the contents of trace elements, nitrogen, and sulphur in relation to an increase in the amount of sludge in the briquettes, which, for the briquettes made from sewage sludge, was nearly twice as high as for the briquettes made from the mixtures. The results of the flue gas analysis for the briquettes with sawdust and wood chip additives were very similar. The briquettes made from sewage sludge with lignocellulosic materials (bark and wood chips) had fuel properties similar to woody biomass, with a calorific value and heat of combustion of 15–16 MJ/kg. Fibrous additives (straw) significantly increased the strength parameters of the briquettes, by more than 50% of the value. The compositions and properties of the mixtures affected the following briquetting parameters: temperature and compressive force. The briquettes made from sewage sludge and additives can be classified according to ISO 21640 as SRFs (solid recovered fuels). In most of the results, the net calorific value (NCV) was 3 to 4; the chlorine content (CL) was 2 to 1; and the mercury content (Hg) was 1. The sewage sludge mixtures facilitated the agricultural and energy use of the briquettes. Full article

One-stage synthesis technology for preparing carbon adsorbents with tailored porosity from agricultural waste is worthwhile due to their extensive application value. Thermal gravimetric analysis, low-temperature N₂ adsorption, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and Raman spectroscopy were used to record the structure transformations of carbon materials, namely pore development, proceeding in the course of the step-wise pyrolysis of renewable and low-cost raw materials such as walnut shells (WNSs), which was carried out within a temperature range of 240–950 °C in a CO₂ flow. The minimum threshold carbonization temperature for preparing nanoporous carbon materials from WNSs, determined by the examination of the N₂ adsorption data, was 500 °C. The maximum specific micropore volume and BET surface achieved in the process without holding a material at a specified temperature were only 0.19 cm³/g and 440 m²/g, respectively. The pyrolysis at 400–600 °C produced amorphous sp² carbon. At a temperature as high as 750 °C, an increase in the X-ray reflection intensity indicated the ordering of graphite-like crystallites. At high burn-off degrees, the size of coherently scattering domains becomes smaller, and an increased background in X-ray patterns indicates the destruction of cellulose nanofibrils, the disordering of graphene stacks, and an increase in the amount of disordered carbon. At this stage, pores develop in the crystallites. They are tentatively assigned to crystallites with sizes of 15–20 nm and to micropores. According to the Raman spectra combined with the XRD and SAXS data, the structure of all the pyrolysis products is influenced by the complex structure of the walnut shell precursor, which comprises cellulose nanofibrils embedded in lignin. This structure was preserved in the initial stage of pyrolysis, and the graphitization of cellulose fibrils and lignin proceeds at different rates. Most of the pores accessible for gas molecules in the resulting carbon materials are associated with former cellulose fibrils. Full article

Abiotic humification, dominated by catalytic oxidation, is one of the critical mechanisms for organic carbon preservation in nature. However, the effects of biochar catalysis on abiotic humification have not yet been elucidated. This study investigated the catalytic power of biochar from walnut shells at different temperatures (300 °C, 600 °C, and 900 °C) for the abiotic transformation of hydroquinone (HQ) as a representative polyphenol. All the biochar samples catalyzed HQ polymerization, resulting in the formation of humic polymers such as fulvic acids (FAs) and humic acids (HAs). Light and oxygen promoted HA formation. HO^• was detected in the BC600–HQ reaction system, and HO^• quenching resulted in a 41.22% decrease in HA production, indicating that HO^• plays a major role in the oxidative polymerization. In the proposed pathway for the abiotic humification, biochar active sites and generated reactive oxygen species accept an electron from HQ, resulting in oxidation to (semi)quinone radicals, which subsequently undergo cleavage or a coupling reaction to form the oligomerized products. Under BC600 catalysis, the weight-average molecular weight (Mw) of the reaction products of HQ, glucose, and glycine reached 14,449 Da. These findings provide new insights into the application potential of biochar for promoting soil carbon sequestration. Full article