An Integrated Process Intensification (IPI) technology-based roadmap is proposed for the utilization of renewables (water, air and biomass/unavoidable waste) in the small-scale distributed production of the following primary products: electricity, H-2, NH3, HNO3 and symbiotic advanced (SX) fertilizers with CO2 mineralization capacity to achieve negative CO2 emission. Such a production platform is an integrated intensified biorefinery (IIBR), used as an alternative to large-scale centralized production which relies on green electricity and CCUS. Hence, the capacity and availability of the renewable biomass and unavoidable waste were examined. The critical elements of the IIBR include gasification/syngas production; syngas cleaning; electricity generation; and the conversion of clean syngas (which contains H-2, CO, CH4, CO2 and N-2) to the primary products using nonthermal plasma catalytic reactors with in situ NH3 sequestration for SA fertilizers. The status of these critical elements is critically reviewed with regard to their techno-economics and suitability for industrial applications. Using novel gasifiers powered by a combination of CO2, H2O and O-2-enhanced air as the oxidant, it is possible to obtain syngas with high H-2 concentration suitable for NH3 synthesis. Gasifier performances for syngas generation and cleaning, electricity production and emissions are evaluated and compared with gasifiers at 50 kWe and 1-2 MWe scales. The catalyst and plasma catalytic reactor systems for NH3 production with or without in situ reactive sequestration are considered in detail. The performance of the catalysts in different plasma reactions is widely different. The high intensity power (HIP) processing of perovskite (barium titanate) and unary/binary spinel oxide catalysts (or their combination) performs best in several syntheses, including NH3 production, NOx from air and fertigation fertilizers from plasma-activated water. These catalysts can be represented as BaTi1-vO3-x{#}(y)N-z (black, piezoelectric barium titanate, bp-{BTO}) and (M3-jMkO4-m)-M-(1)-O-(2){#}(n)N-r/SiO2 (unary (k = 0) or a binary (k > 0) silane-coated SiO2-supported spinel oxide catalyst, denoted as M/Si = X) where {#} infers oxygen vacancy. HIP processing in air causes oxygen vacancies, nitrogen substitution, the acquisition of piezoelectric state and porosity and chemical/morphological heterogeneity, all of which make the catalysts highly active. Their morphological evaluation indicates the generation of dust particles (leading to porogenesis), 2D-nano/micro plates and structured ribbons, leading to quantum effects under plasma catalytic synthesis, including the acquisition of high-energy particles from the plasma space to prevent product dissociation as a result of electron impact. M/Si = X (X > 1/2) and bp-{BTO} catalysts generate plasma under microwave irradiation (including pulsed microwave) and hence can be used in a packed bed mode in microwave plasma reactors with plasma on and within the pores of the catalyst. Such reactors are suitable for electric-powered small-scale industrial operations. When combined with the in situ reactive separation of NH3 in the so-called Multi-Reaction Zone Reactor using NH3 sequestration agents to create SA fertilizers, the techno-economics of the plasma catalytic synthesis of fertilizers become favorable due to the elimination of product separation costs and the quality of the SA fertilizers which act as an artificial root system. The SA fertilizers provide soil fertility, biodiversity, high yield, efficient water and nutrient use and carbon sequestration through mineralization. They can prevent environmental damage and help plants and crops to adapt to the emerging harsh environmental and climate conditions through the formation of artificial rhizosphere and rhizosheath. The functions of the SA fertilizers should be taken into account when comparing the techno-economics of SA fertilizers with current fertilizers.

Thallium (Tl) is a highly toxic element and can accumulate in human body through food, water, or air and cause damage to multiple organs. In this study, the nonthermal plasma (NTP) was employed to irradiate the potassium dihydrogen phosphate (KH2PO4) and sodium diethyldithiocarbamate trihydrate (SDDC) to solve the issues brought by their poor stability and insufficient chelation capabilities in soils to intensify their performance on immobilizing monovalent Tl contaminants in soils. Both an orthogonal design (OD) and a central composite design (CCD) were adopted to arrange the multi-parametrical modification and stabilization experiments. The leaching toxicities ranging from 5.11 to 52.37 mu g/L of Tl+ ions were obtained in the OD experiments. The changes in both NTP time and the molar ratios of KH2PO4 to SDDC had a significant effect on the activation procedure. The leaching concentration ranging from 0.37 to 7.34 mu g/L was achieved in the CCD stabilization experiments. NTP activation and the rearrangement of the stabilization conditions both were beneficial to the transformation of physicochemical states of Tl pollutants in soils, which proved the existence of chemical immobilization brought by the irradiated stabilizers (NTP-PK-SDDCs) to the Tl contaminants. The stabilization process was targeted between only Tl contaminants and NTP-PK-SDDCs in soils. The NTP irradiation enhanced the physicochemical characteristics of stabilizers, further intensifying the immobilization of Tl species in the soils. The enhancement mechanism was attributed to the free radicals-induced doping, oxidation, and polycondensation and the bombards of electrons, which strengthened the electrostation and chemisorption of NTPPK-SDDCs towards Tl ions. The potential impact of this study includes the development of more effective and sustainable remediation methods for Tl-contaminated soils, contributing to environmental protection and human health.