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Nitrogen (N) is a critical nutrient that is essential for plant growth and sustainable population development. Since the inception of modern fertilizer technology, N has been supplied to the environment via low-stability fertilizer materials which has resulted in very large losses of reactive nitrogen to the environment. These losses have severe impacts on soil, air and surface water locally and result in changes to the ecosystem biodiversity as well as climate globally. Synthesis of nitrogen fertilizer, such as urea, consumes 1–2 % of global energy as well as significant amounts of natural gas. Therefore, it is necessary to improve the stability of fertilizer-N in the environment to decrease their losses and increase N-use efficiency.This work provides a critical evaluation of the current and emerging methods to stabilize urea fertilizers to deliver nitrogen to the environment more sustainably. The emphasis in this review is placed on material chemistry development, such as recent emergence of urea cocrystals that possess reduced solubility and enhanced environmental stability. The materials analysis suggests that future research needs to focus on urea stabilization methods that create partial bonds between the constituents beyond weak molecular interaction. This requires avoiding unsustainable feedstock, such as formaldehyde, or exogenous stabilizing molecules that affect the soil biota, such as urease inhibitors. These developmental products then need to be transformed into thriving technologies to provide high-value fertilizers by decreasing the energy footprint needed to make ammonia, a precursor of urea.

The growing demand for renewable energy has generated interest in biofuels as alternatives to fossil fuels. Second-generation biofuels, derived from deoxygenating fats and oils, have garnered a higher level of interest from industry and academia due to their potential for direct replacement of diesel and jet fuels. Palm oil, mostly cultivated in Thailand and composed of C16 and C18 fatty acids, is a primary feedstock sought for biofuel production. Palm oil deoxygenation contains several pathways that may or may not require hydrogen gas. This study aimed to produce biofuels in different fuel ranges, such as gasoline, jet fuel, and diesel, through palm oil deoxygenation using glycerol as a hydrogen source. Glycerol, a low-value byproduct, was used as a hydrogen donor, whereas nickel-molybdenum-supported catalysts were chosen for their high efficiency in deoxygenation and cost-effectiveness. The study investigated the impact of reaction time, temperature, and catalyst activation method on palm oil deoxygenation. Catalyst characterization methods, including XRD, SEM, TEM, XPS, FTIR, TGA, and nitrogen-sorption, were employed to understand the role of catalysts’ activity during palm oil upgrading. Findings indicated that alkane hydrocarbons are the major components in liquid products. The presence of excess hydrogen in post reaction gaseous phase proves the hydrogen donation capability of glycerol. Increased reaction time and temperature facilitated the removal of oxygen from palm oil. Nickel-molybdenum on zirconia activated by sulfidation demonstrated higher stability than by reduction activation.

Urea cocrystal materials are a potential fertilizer source that has shown to decrease environmental nitrogen losses. Novel nitrogen (N)-containing urea cocrystal fertilizers, CaSO4·4urea (UC1) and Ca(H2PO4)2·4urea (UC2), were synthesized using the mechanochemical method to form stable urea cocrystals to be tested as a fertilizer source for turfgrass. The objectives of this study were to 1) evaluate the response of ‘Tifway’ hybrid bermudagrass (Cynodon dactylon × C. traansvalensis Burt Davy) to N fertilization by urea cocrystals and traditional coated urea products (MU·PCU, methylene urea, urea, polymer-coated urea; PCU, polymer-coated urea, urea) supplied at two rates at the beginning of two, 10-week study periods conducted under a greenhouse setting and 2) investigate N release behavior of urea and two cocrystal products using a rapid water release test. In the turfgrass response study conducted in the greenhouse, improved turfgrass quality above the minimum quality threshold was observed when averaging across all products. For normalized difference vegetation index (NDVI), cocrystal outperformed all other products in the summer study and both cocrystal products outperformed the traditional product (MU·PCU) in the winter study. Further, both cocrystal products showed favorable growth responses compared with the commercial products provided by positive clipping production and vertical extension rates. In the nitrogen release experiment, a rapid water release test revealed the N release peak of urea was significantly higher than both UC1 and UC2. Furthermore, significantly higher N was leached from urea (15% loss) compared with both UC1 and UC2 (≈8% loss). Results from both studies provide evidence supporting suitability of urea cocrystal application on bermudagrass and potential as a slow-release fertilizer source through sustained turfgrass vigor, growth, decreased N release peak, and decreased leaching losses.

The excessive mineralization of organic molecules during anaerobic fermentation increases the availability of nitrogen and carbon. For this reason, the development of downstream processing technologies is required to better manage ammonia and carbon dioxide emissions during the storage and land application of the resulting soil organic amendment. The present work investigated classical distillation as a technology for valorizing ammoniacal nitrogen (NH4+-N) in anaerobic digestate. The results implied that the direct isolation of ammonium bicarbonate (NH4HCO3) was possible when applying the reactive distillation to the food waste digestate (FWD) with a high content of NH4+-N, while the addition of antifoam to the agrowaste digestate (AWD) was necessary to be able to produce an aqueous solution of NH4HCO3 as the distillate. The reason was that the extraction of NH4HCO3 from the AWD required a higher temperature (>95 °C) and duration (i.e., steady state in batch operation) than the recovery of the inorganic fertilizer from the FWD. The titration method, when applied to the depleted digestate, offered the quickest way of monitoring the reactive distillation because the buffer capacity of the distillate was much higher. The isolation of NH4HCO3 from the FWD was attained in a transient mode at a temperature below 90 °C (i.e., while heating up to reach the desired distillation temperature or cooling down once the batch distillation was finished). For the operating conditions to be regarded as techno-economically feasible, they should be attained in the anaerobic digestion plant by integrating the heat harvested from the engines, which convert the biogas into electricity.

Water pollution is a major concern due to its detrimental effects on the environment and public health. The particular danger of inorganic pollutants arises from their persistent toxicity and inability to biodegrade. Recently, electrocoagulation (EC) has been demonstrated as an alternative sustainable approach to purifying wastewater due to the increasingly strict pollution prevention rules. In particular, EC has been used to remove inorganic pollutants, such as Cr, Zn, Pb, or As. EC has emerged as a sustainable tool for resource recovery of some inorganic pollutants such as N and P that, when recovered, have value as plant nutrients and are critical in a circular economy. These recovered materials can be obtained from diverse agricultural drainage water and recycled as fertilizers. In this work, a state-of-the-art technique is reviewed describing the advances in contaminant removal and nutrient recovery using EC through an in-depth discussion of the factors influencing the contaminant removal process, including operating pH, time, power, and concentration. Furthermore, limitations of the EC technology are reviewed, including the high-power consumption, fast deterioration of the sacrificial electrodes, and the types of contaminants that could not be efficiently removed. Finally, new emerging constructs in EC process optimization parameters are presented.

It is often assumed in X-ray Photoelectron Spectroscopy that binding energy shifts are synonymous with changes in the chemical state of an atom and the chemical state can be described in terms of oxidation state and stoichiometry of the elements in a material that correlates with photoemission peaks. However, when an atom is bonded into a crystal lattice, the shapes and binding energy of photoemission may not match the expected stoichiometry when measured by XPS, even though shifts in binding energy suggest new oxidation states. In this work, a set of experiments is presented, in which Ar+ and He+ ions of different energies modify the native oxide on a titanium foil which yields XPS spectra that are not easily open to analysis by conventional peak models. In the course of analyzing these complex photoemission data by linear algebraic methods, the prospect emerged that XPS is suggesting that sputtering a native oxide may be providing insight into structural perturbation in addition to the stoichiometry-type changes to the native oxide.

Complex inorganic powders based on calcium phosphates have found a plethora of practical applications. Of particular interest are the CaO-P2O5 system-based multi-component material powders and granules as the source of major- and micronutrients for the plants. The emerging strategy is to use nano fertilizers based on hydroxyapatite (HAP) for phosphorus and other nutrient delivery. The doping of micronutrients into HAP structure presents an interesting challenge in obtaining specific phase compositions of these calcium phosphates. Various techniques, including mechanochemical synthesis, have been employed to fabricate doped HAP. Mechanochemical synthesis is of particular interest in this review since it presents a relatively simple, scalable, and cost-effective method of calcium phosphate powder processing. The method involves the use of mechanical force to promote chemical reactions and create nanometric powders. This technique has been successfully applied to produce HAP nanoparticles alone, and HAP doped with other elements, such as zinc and magnesium. Nanofertilizers developed through mechanochemical synthesis can offer several advantages over conventional fertilizers. Their nanoscale size allows for rapid absorption and controlled release of nutrients, which leads to improved nutrient uptake efficiency by plants. Furthermore, the tailored properties of HAP-based nano fertilizers, such as controlled porosity and degradation levels, contribute to their effectiveness in providing plant nutrition.

Despite numerous tutorials and standards written to the technical community on X-ray photoelectron spectroscopy (XPS), difficulties with data acquisition, analysis, and reporting persist. This work focuses on common errors in XPS that are frequently observed in the scientific literature and their sources. Indeed, this work covers: (i) XPS data collection, initial data analysis, and data presentation, (ii) Handling XPS backgrounds, (iii) Common errors in XPS peak fitting, and (iv) XPS data presentation and reporting. Graphical examples of errors and appropriate ways of handling data and correcting errors are provided. Additional readings are listed for greater in-depth exploration of the subjects discussed.

Principal component analysis (PCA), as applied to the processing of the complex X-ray photoelectron spectroscopy (XPS) lineshapes, is discussed. PCA analysis example is provided of complex native iron oxide films on Fe foil XPS spectra further modified by argon and helium ion beams. Abstract PCA components are derived from Fe 2p, O 1 s and C 1 s regions leading to the assignments of surface (oxy)hydroxide, Fe2O3, FeO and Fe metal, as corroborated by the corresponding elemental quantification profiles. Detailed mathematical concepts behind PCA analysis of spectra data are provided.

Efficient treatment of nutrient-rich wastewater is of paramount importance for protecting the ecosystem. In this work, an efficient, abundant, and eco-friendly adsorbent was derived from biochar and employed for phosphorus (P) adsorption. The key factors influencing the P removal efficiency of the activated biochar, including P concentration, pH, dosage, temperature, adsorption time, and influence of co-existing ion type, were investigated. Maximum P adsorption percentage (100%) was obtained with 10 mg/L and zinc chloride activated biochar (BC–Zn) compared to the other activated biochars. Results show that by increasing the P concentration from 5 to 200 mg/L, the phosphorus adsorption capacity increases from 0.13 to 10.4 mg/g biochar. Isotherms and kinetic studies further show that the P adsorption follows the Langmuir and quasi-second-order kinetic models. The mechanistic investigation demonstrated that P adsorption occurred by precipitation reaction. Furthermore, P desorption has been studied at different time intervals to understand the P release rate after adsorption.

Urea, a basic chemical compound, holds diverse applications across numerous domains, ranging from agriculture to energy storage. Of particular interest is its role as a hydrogen bond donor (HBD). This specific characteristic has propelled its utilization as an essential component in crafting deep eutectic solvents (DESs) for battery electrolytes. Incorporating urea into DESs presents a promising avenue to address environmental concerns associated with traditional electrolytes, thereby advancing battery technology. Conventional electrolytes, often composed of hazardous and combustible solvents, pose significant environmental risks upon improper disposal potentially contaminating soil and water and threatening both human health and ecosystems. Consequently, there is a pressing need for eco-friendly alternatives capable of upholding high performance and safety standards. DESs, categorized as organic salts resulting from the blending of two or more compounds, have emerged as promising contenders for the next generation of electrolytes. Urea stands out among DES electrolytes by enhancing ion transport, widening the electrochemical window stability (ESW), and prolonging battery cycle life. Further, its non-toxic nature, limited flammability, and elevated thermal stability play pivotal roles in mitigating environmental concerns and safety issues associated with traditional electrolytes. Laboratory testing of urea-based DES electrolytes across various battery systems, including Al-ion, Na-ion, and Zn-ion batteries, has already been demonstrated. This review examines the evolution of urea-based DES electrolytes by elucidating their structure, molecular interaction mechanisms, performance attributes, and preparation methodologies.

A capacitive micromachined ultrasound transducer (CMUT) was engineered and functionalized with zeolitic imidazolate framework-8 (ZIF-8) dispersed in a photoresist AZ1512HS (AZ) matrix to function as a gravimetric gas sensor. The sensor response was recorded in the presence of nitrogen, argon, carbon dioxide, and methane gases as well as water, acetylene, a propane/butane mixture, n-hexane, gasoline, and diesel vapors. The photoresist matrix alone was found to have a negligible response to all the gases and vapors, except for water vapor. No visible difference in sensor response was detected when switching from nitrogen to methane gas. However, a strong shift in the sensor resonance frequency was observed when exposed to higher hydrocarbons, ranging from 1 kHz for acetylene to 7.5 kHz for gasoline. Even longer-chain hydrocarbons, specifically kerosene and more so diesel, had a significantly reduced sensor frequency shift compared with gasoline. Sensors functionalized with a thin film of AZ+ZIF-8 demonstrated higher sensitivity in their response to a hydrocarbon molecular mass than without functionalization.

Water organic pollution has become a major issue. A large number of people suffer from the decline in water quality. In addition, polluted water can lead to health problems or excessive deaths. In this regard, an increasingly important method for efficient water treatment is electrocoagulation (EC), the technology that encompasses a small equipment size combined with a simple operation compared to other water treatment methods. The importance of EC is especially accentuated by the recent decarbonization efforts due to the increasing availability of renewable electricity systems. This review provides an overview of the most recent developments in EC technology as it pertains to wastewater treatment. The EC is preferred for organic wastewater treatment over other traditional treatment methods due to its easy setup and low material costs. Moreover, the EC is very powerful in destabilizing organic impurities by charge neutralization and then coagulating to form flocs. In addition, EC has shown high efficiency not only in removing various organic pollutants but also in emerging persistent contaminants, such as microplastics. For these reasons, the EC mechanisms and related functional modalities are reviewed, as well as extensive details are provided on the diversity of the removed contaminants. Overall, this review provides significant new knowledge of interest for environmental chemical researchers in particular and engineers in general on the details of the EC technology for wastewater treatment and water purification.

Ammonium carbonates are a group of fertilizer materials that include ammonium bicarbonate, ammonium carbonate hydrate, and ammonium carbamate. They can be synthesized from diverse nutrient-bearing liquid waste streams but are unstable in a moist environment. While extensively utilized several decades ago, their use gradually decreased in favor of large-scale, facility-synthesized urea fertilizers. The emergence of sustainable agriculture, however, necessitates the recovery and reuse of nutrients using conventional feedstocks, such as natural gas and air-derived nitrogen, and nutrient-containing biogenic waste streams. To this extent, anaerobic digestion liquid presents a convenient source of solid nitrogen and carbon to produce solid fertilizers, since no significant chemical transformations are needed as nitrogen is already present as an ammonium ion. This review describes detailed examples of such feedstocks and the methods required to concentrate and crystallize solid ammonium carbonates. The technologies currently proposed or utilized to stabilize ammonium carbonate materials in the environment are described in detail. Finally, the agricultural efficiency of these materials as nitrogen and carbon source is also described.

Organophosphates have been identified as an emerging group of contaminants in wastewater with significant negative human health effects. Due to their persistence in the watershed, soil, and the food chain, their degradation during wastewater treatment and before the release has garnered significant interest. Advanced oxidation processes enable the degradation of organophosphates with high conversion and fast kinetics. Photo-Fenton and photo-Fenton-like processes utilize a light source to initiate the Fenton reaction and produce reactive oxygen species that are required for the reaction propagation. While homogeneous catalysts have been studied extensively, heterogeneous catalysts are emerging due to their ease of use, separation, and recycling. This review provides a summary of the current progress made in the field of organophosphate degradation using a heterogeneous photo-Fenton-like process when compared to the homogeneous process and highlights the need for the rational photocatalyst design as well as suggests future directions of research, including utilizing wastewater feeds that represent real-world compositional complexity as well as providing molecular-level catalytic process insights to better understand limitations of these catalysts.

The methodology presented within this work is a result of years of interactions between many junior and senior X-ray Photoelectron Spectroscopy (XPS) users operating within the CasaXPS spectral processing and interpretation program framework. In particular, discussions arising from a series of workshops have been a significant source for developing the overall XPS data processing concept and are the motivation for creating this work. These workshops organized by the Institut des Matériaux Jean Rouxel (IMN), Nantes gather both experienced and novice users of XPS for a week of discourse in conceptual experiment design and the resulting data processing. However, the framework constructed and utilized within these workshops encouraged the dissemination of knowledge beyond XPS data analysis and emphasized the importance of a multi-disciplinary collaborative approach to surface analysis problem-solving. The material presented here embodies data treatment originating from data made available to the first CNRS Thematic Workshop presented at Roscoff 2013. The methodology described here has evolved over the subsequent workshops in 2016 and 2019 and currently represents the philosophy used in CasaXPS spectral data processing paradigm.

Extensive application of mineral fertilizers resulted in high soil acidity, which is one of the major problems for crop production and soil degradation. Industrial solid waste, such as lime kiln dust and wood ash, can be used as alternative liming materials to benefit sustainable agricultural development. In this work, pelletized lime kiln dust with and without wood ash was utilized as liming material and the results of the three-year field study were compared with conventional mineral-based liming materials. It was determined that pelletized lime kiln dust satisfies the requirements posed by the recent European Union regulations to qualify as liming materials. The application of 2000 kg/ha Ca equivalent pelletized lime kiln dust increased soil pHKCl by ~0.55 pH units. Moreover, pelletized lime kiln dust significantly increased spring wheat grain yields ranging from 33.6% to 40.4%, depending on the pellet size. The usage of these liming materials not only increased crop yield but also decreased heavy metal concentration in soil. Due to high alkalinity, carbonate content, easy handling, and the transportation of pelletized lime kiln dust with and without wood ash, the materials have the potential to be used in agriculture as liming materials to reduce soil acidification and increase crop productivity or be used as soil amendments.

The use of major nutrient-containing solid residuals, such as recycled solid waste materials, has a strong potential in closing the broken nutrient cycles. In this work, biofuel ash (BA) combined with green waste compost (GWC) was used as a nutrient source to improve soil properties and enhance wheat and triticale yields. The main goal was to obtain the nutrient and heavy metal release dynamics and ascertain whether GWC together with BA can potentially be used for concurrent bioremediation to mitigate any negative solid waste effects on the environment. Both BA and GWC were applied in the first year of study. No fertilization was performed in the second year of the study. The results obtained in this work showed the highest spring wheat yield when the GWC (20 t ha−1) and BA (4.5 t ha−1) mixture was used. After the first harvest, the increase in the mobile forms of all measured nutrients was detected in the soil with complex composted materials (GWC + BA). The content of heavy metals (Cd, Zn, and Cr) in the soil increased significantly with BA and all GWC + BA mixtures. In both experiment years, the application of BA together with GWC resulted in fewer heavy metals transferred to the crops than with BA alone.

Air pollution is a risk factor for respiratory infections, and one of its main components is particulate matter (PM), which is comprised of a number of particles that contain iron, such as coal fly ash (CFA). Since free iron concentrations are extremely low in airway surface liquid (ASL), we hypothesize that CFA impairs antimicrobial peptides (AMP) function and can be a source of iron to bacteria. We tested this hypothesis in vivo by instilling mice with Pseudomonas aeruginosa (PA01) and CFA and determine the percentage of bacterial clearance. In addition, we tested bacterial clearance in cell culture by exposing primary human airway epithelial cells to PA01 and CFA and determining the AMP activity and bacterial growth in vitro. We report that CFA is a bioavailable source of iron for bacteria. We show that CFA interferes with bacterial clearance in vivo and in primary human airway epithelial cultures. Also, we demonstrate that CFA inhibits AMP activity in vitro, which we propose as a mechanism of our cell culture and in vivo results. Furthermore, PA01 uses CFA as an iron source with a direct correlation between CFA iron dissolution and bacterial growth. CFA concentrations used are very relevant to human daily exposures, thus posing a potential public health risk for susceptible subjects. Although CFA provides a source of bioavailable iron for bacteria, not all CFA particles have the same biological effects, and their propensity for iron dissolution is an important factor. CFA impairs lung innate immune mechanisms of bacterial clearance, specifically AMP activity. We expect that identifying the PM mechanisms of respiratory infections will translate into public health policies aimed at controlling, not only concentration of PM exposure, but physicochemical characteristics that will potentially cause respiratory infections in susceptible individuals and populations.