Salt-affected soils in the Mediterranean are difficult to reclaim under organic farming, where amendment options are limited, and hydrology strongly controls salt redistribution. In an oat-triticale-barley-oat rotation, we evaluated different amendments (control, gypsum - G3, gypsum plus sulphur - G3S1, G6S2, gypsum plus farmyard manure (FYM) - G6 + OM, and gypsum plus sulphur plus FYM - G3S1 + OM) and tillage (discing and discing plus ripping) interventions on a saline-sodic Anthrosol in the Rasa valley, Croatia. Crop yields were recorded annually, and soil physical and chemical properties were determined at the beginning and end of the trial. Gypsum significantly increased exchangeable Calcium (Ca) and reduced exchangeable sodium percentage (ESP). At the end of the experiment, electrical conductivity (EC) decreased significantly. Water-stable aggregates (WSA) increased significantly in all plots with added amendments, while the control plots showed the poorest structure. Ripping generally lowered bulk density and penetration resistance compared with discing, but effects were treatment- and depth-specific. Yield benefits became most evident in the last two years: barley yield was significantly lower in the control than in all amended treatments, and oat yield was 26-50% higher in G6S2, G3S1 + OM, and G6 + OM than in the control. Overall, the results indicate that gypsum-based amendments, particularly when combined with FYM, can progressively improve soil condition and crop performance under organic management, while the benefits of deep loosening remain more variable and dependent on seasonal soil conditions.
Industry decarbonization is a priority to mitigate climate change. Cement production is a hard-to-abate sector responsible for 7% of emissions, for which hydrogen has been proposed to reduce energy-related emissions. However, storage remains a critical challenge as conventional approaches require extreme operating conditions. LOHCs may overcome this limitation by allowing ambient storage compatible with existing fossil infrastructure. This work presents a novel integration of LOHCs with a hybrid CHP (SOFC and hydrogen turbine) in the cement process, considering both technical and performance indicators. Two configurations were studied to supply: (a) hydrogen only, and (b) hydrogen and power. Exhaust heat from CHP and cement process was proposed to meet the dehydrogenation thermal demand. LOHCs dehydrogenation and CHP were modeled using first-principles models. A multiobjective optimization was formulated to minimize CAPEX while maximizing LOHCs utilization efficiency. This problem included continuous and discrete variables, resulting in a mixed-integer nonlinear programming (MINLP) problem. Given the high computational cost, a surrogate-based optimization strategy was adopted. Common regression and classification models were trained on a dataset generated via maximin Latin Hypercube sampling. Reactor operating conditions, LOHCs feed and catalyst use were the decision variables. The final design reached for Cases (a) and (b) 53.82% and 50.66% LOHCs utilization efficiency, defined as the fraction of LOHCs-stored hydrogen converted into power and fuel for the cement process, with CAPEX of 1.58 and 3.37 MM$/MW respectively, covering the dehydrogenation process and CHP module. Integrating LOHCs with cement production and CHP reduced dehydrogenation energy losses. This positions LOHCs as a promising route toward cement sector decarbonization.
Sheep manure is an abundant biogenic residue with potential as a renewable feedstock for producing valueadded materials through thermochemical conversion. This study investigates the valorisation of sheep manure by slow pyrolysis to obtain a bio-oil suitable for use as a bio-based modifier in bituminous binders. Physicochemical characterisation showed that the recovered BO had a pH of 4.8, 2.20 wt% water, and 30.33 wt% oxygen, with ketones dominating the GC-MS profile. The sheep-manure-derived bio-oil was incorporated into a conventional B50/70 bitumen at 3, 6, and 9 wt%, and its performance was compared with that of a commercial additive. The modified binders were evaluated using dynamic shear rheometer, multiple-stress creep-recovery, linear amplitude sweep, binder yield energy, and elastic recovery tests, supported by Burgers-model fitting. The bio-oil produced a clear dosage-dependent softening effect, reducing the complex modulus, complex viscosity, and elastic contribution of the binder. At 20 degrees C, the complex modulus decreased by 56% for the 3 wt% formulation and by 81% for the 9 wt% formulation compared with the base binder. High bio-oil contents increased accumulated deformation and strongly reduced recovery capacity, particularly under multiple-stress creep-recovery conditions, indicating lower resistance to permanent deformation. Intermediate-temperature tests also showed that 6 and 9 wt% bio-oil reduced mechanical resistance and recovery capacity, whereas the 3 wt% dosage provided a more balanced viscoelastic response. Slow pyrolysis of sheep manure therefore represents a promising circular route for producing a value-added bio-based modifier for bituminous binders, particularly at moderate dosages that balance softening efficiency and rheological performance.
Supercritical water gasification is an advanced and promising technology for sewage sludge treatment that simultaneously removes hazardous contaminants and recovers valuable resources. Its harsh operating conditions and complex process dynamics necessitate systematic risk assessment. Conventional failure mode and effects analysis (FMEA) methods face critical limitations, including unreliable expert evaluations due to cognitive uncertainty and insufficient consideration of interactions among risk factors. To address these gaps, this study develops an enhanced outranking-based FMEA framework integrating dual spherical fuzzy rough number clouds to model uncertainty, subjectivity, data insufficiency, and randomness inherent in expert assessments. The framework provides a rigorous mechanism for identifying potential failures and estimating their impacts across the system lifecycle. An extended best-worst method (BWM) with a min-max nonlinear optimization structure derives the risk factor weights, ensuring consistent and discrimination-preserving values using a consistency ratio test. To reduce the cognitive burden of extensive pairwise comparisons, the relative importance of each risk factor is determined by comparing it with the most and least critical risk factors using cloud-based preference information. An improved ELimination and Choice Translating REality (ELECTRE) III procedure subsequently defines indifference, weak, and strong preference relations using explicitly specified thresholds. Concordance, discordance, and credibility measures generate the final risk rankings, enabling transparent and robust prioritization. The proposed framework is validated using a real-world supercritical water gasification system and cross-validated through an independent wastewater treatment plant case study. Sensitivity, comparative, and ablation analyses further demonstrate its robustness, transferability, and superior performance under complex uncertainty. These findings confirm the framework's technical rigor and practical applicability, offering valuable insights for improving the reliability, sustainability, and resilience of supercritical water gasification systems.
This study investigates spray-paint removal from Rosa Porrino and Vilachan granites, widely used in architectural heritage, using an industrial ytterbium-doped pulsed fibre laser (1064 nm), focusing on the influence of substrate characteristics on cleaning effectiveness and laser-induced surface modifications. A multiscale approach combining petrography, X-ray diffraction, optical microscopy, SEM-EDS and interferometric surface topography correlated cleaning effectiveness with substrate mineralogy, microstructure and surface texture. Near-complete paint removal was achieved for both granites, although higher fluences were required for Vilachan, demonstrating amaterial-dependent cleaning response. Paint residues preferentially persisted within polycrystalline quartz aggregates and surface discontinuities, indicating an influence of substrate microstructure on paint retention. Laser irradiation produced a heterogeneous mineral-scale response: quartz exhibited conchoidal fracture features consistent with brittle fracture, K-feldspar showed increased surface roughness, biotite showed superficial melting and groove-like texturing, while muscovite showed treatment-induced texturisation. These responses were accompanied by measurable changes in surface topography and roughness. The paint ablation threshold exceeded that of the granitic substrate, indicating that laser-substrate interaction may occur before complete paint removal and that a simple fluence window for selective cleaning without substrate modification cannot be assumed. Overall, cleaning effectiveness and selectivity depend on processing conditions, mineralogical composition, microstructural characteristics and surface texture. By integrating cleaning effectiveness with morphological responses and quantified topographical changes at the individual mineral-phase scale in two granites, this comparative, multiscale assessment relates the conditions required for paint removal to the induced surface modifications, providing a material-specific understanding of the balance between paint removal and substrate modification.
