Search Results (46)

Pastoral systems in New Zealand are under societal pressure due to their increasing negative environmental impact in terms of greenhouse gas emissions. This study was conducted to investigate the effects of supplementing a mixture containing hydrolysable and condensed tannins on the in vitro fermentation characteristics and gas production of three different forages, Lolium perenne, Medicago sativa, and Plantago lanceolata. Three fermentation runs of 48 h were conducted using the ANKOM gas production technique, with each pertaining to a particular forage with or without (control) tannin. Tannins were added to the fermentable substrate (i.e., forage) at a level of 0.3%. For each run, rumen fluid was collected from two fistulated Holstein Friesian × Jersey cows. The ANKOM RF gas production modules were used to monitor gas pressure and temperature every 5 min. At the end of each run, the pH of the fluid was measured, gas vials were taken for methane (CH₄) measurements and liquor samples were taken to measure volatile fatty acids (VFA) and NH₃ concentrations. The addition of tannins reduced the fractional rate of gas production for alfalfa (p ≤ 0.04) but increased it for ryegrass and plantain. There was a tendency for reduced gas production for ryegrass when tannins were added (p = 0.10). There was also a tendency for CH₄ production to reduce (p < 0.10) and N₂O to increase (p = 0.10) when tannins were added. Iso-butyrate tended to be lower for ryegrass control than to ryegrass with tannins (p = 0.08). Valerate concentration was lower for plantain control than to plantain with tannins. No effects were detected for gas composition (p > 0.05) or VFA concentrations (p > 0.05) when fermenting alfalfa. Under the condition of this study, these results may suggest that low-level tannin addition to the diet may affect rumen-fermentation pattern with a potential reduction of CH₄ production in Lolium perenne-based diets. Further research is required on the effect of low levels of tannin supplementation under ex vitro and in vivo conditions as tannin supplementation effects might be substrate-dependent. Full article

Transport and vehicle traffic are closely connected with particulate matter (PM) pollution, inducing various fractions into the atmosphere, some of them forming significant deposits on the surface of the car. They are washed away during carwash-inducing slurries collecting the PM deposits, which are characteristic of a large area. Crystalline PM matter was investigated by XRD coupled with polarized optical microscopy (POM). Organic matters were investigated by Fourier-Transform Infrared spectrometry (FTIR) and gas chromatography, GC-MS. Their microstructure and elemental composition were investigated by SEM-EDX. The crystalline features contain mainly quartz, calcite, and clay (muscovite and kaolinite) particles having traces of goethite and lepidocrocite. Slurry particle size distribution was established by sieving on the following meshes: 63 µm, 125 µm, 250 µm, 500 µm, 1000 µm, 2000 µm, and 4000 µm. Coarse fractions of 250–4000 μm are dominated by quartz and calcite particles. The quartz and calcite amount decreases with particle size, while the muscovite and kaolinite amount increases in the finest fractions of 0–125 μm. Organic matter was evidenced, firstly, by FTIR spectroscopy, revealing mostly CH₂; C=O, and NH₄ bonds that are more intense for the fine particulate fractions. The organic deposits form mainly amorphous crusts associated with micro- and nano-plastic particles related to the phthalates and traces of the washing detergents. Atomic Force Microscopy revealed their size range between 60 and 90 nm and evidenced nanoparticles within samples. The nanofractions adhere to the bigger particles in humid environments, assuring their immobilization to reduce their hazardous potential. Carwash slurry blending with fertile soil ensures proper grass seed germination and growth at mixtures of up to 60% slurry, allowing its sustainable reconversion as soil for landfill and dump rehabilitation, preventing the PM emission hazard. Blended compositions containing more than 60% slurry have noxious effects on the grass seeds, inhibiting their germination. Full article

The reduction of hematite with ammonia is a potentially environmentally friendly method of ironmaking. Previous studies on ammonia reduction of pellets typically involved samples weighing only 2.8 g and lacked detailed activation energy analysis for the ammonia-hydrogen co-reduction of pellets. Therefore, to further investigate the reduction thermodynamics and kinetics of NH₃–H₂ reduction of pellets, this study uses 50 g pellets for reduction experiments. By increasing the pellet mass, the study expands the scope of kinetic research on ammonia reduction of pellets. The results indicate that nitrogen gas produced from ammonia decomposition reduces the equilibrium components of the reducing gas. In the temperature range of 700–850 °C, the formation of iron nitride exhibits a narrow range during ammonia reduction of hematite. In the reduction of 50 g of pellets, the reduction rate using 100% NH₃ is lower than that using a 50% NH₃ and 50% H₂ mixed gas, which is, in turn, slower than using 100% H₂. As temperature increases, the reduction effect of 50% NH₃ and 50% H₂ approaches that of 100% H₂. Among common gas-solid reaction mathematical models, the Phase-boundary-controlled model with the Contracting Cylinder Model is selected as the most plausible mechanistic function. For the reduction of 50 g of pellets, the activation energies for reactions using 100% NH₃, 50% NH₃ and 50% H₂, and 100% H₂ are 65.42, 54.37, and 29.17 kJ/mol, respectively. The decomposition of NH₃ has a negative effect on the reduction of Fe₂O₃. XRD analysis and electron microscopy element line scanning show that Fe₄N is formed during the reduction of Fe₂O₃ with 100% NH₃. The use of a 50% NH₃ and 50% H₂ mixture significantly reduces the formation of Fe₄N during the reduction of the pellets. Full article

Currently, less attention is paid to zinc–carbon batteries, although they are still widely used and are among the major types of batteries collected and recycled. The recycling technologies currently in use do not allow the complete recovery of resources, are not self-sufficient and require additional financing. Therefore, this paper aims to study the possibility of complete recycling of waste zinc–carbon batteries and to suggest the practical use of the final products generated in the recycling process. The possibility of complex processing of spent zinc–carbon batteries using mechanical separation and processing of the battery’s components (steel case, zinc electrode, graphite electrode, polypropylene and paper insulators) is justified. The separation of spent electrolytes from other components of batteries with hydrochloric acid was studied. It was shown that the extraction of Zn²⁺ and NH⁴⁺ cations takes place following the addition of an equivalent amount of Na₃PO₄ solution and water-insoluble NH₄ZnPO₄ salt sedimentation. Waste agglomerate (mixture of MnO₂, MnO(OH), and graphite) was regenerated to its initial composition (MnO₂, graphite) at a temperature of 300–325 °C; manganese (III) hydroxide was oxidized to manganese (IV) dioxide. Thermal destruction of polypropylene and paper insulators with additional introduction of polyethylene into the primary mixture produced pyrolysis liquid, pyrocarbon and pyrolysis gas as products. The practical use of the products obtained and compliance with the environmental requirements of the suggested method of waste batteries recycling were shown. Full article

We have developed a convenient route to transform biomass power plant ashes (BPPA) into porous sponge-like fertilizer composites. The absence of water prevents the chemical reaction and carbon dioxide formation when concentrated sulfuric acid is mixed with BPPA and CaCO₃. Adding water, however, initiates the protonation reaction of carbonate ion content and starts CO₂ evolution. The key element of the method was that the BPPA and, optionally, CaCO₃ and/or CaSO₄·0.5H₂O were mixed with concentrated sulfuric acid to make a paste-like consistency. No gas evolution occurred at this stage; however, with the subsequent and controlled addition of water, CO₂ gas evolved and was released through the channels developed in the pastry-like material due to the internal gas pressure, but without foaming. Using a screw-containing tube reactor, the water can be introduced under pressure. Due to the pressure, the pores in the pastry-like material became smaller, and consequently, the mechanical strength of the granulated and solidified mixture became higher than that of the reaction products prepared under atmospheric pressure. The main reaction products were syngenite (K₂Ca(SO₄)₂·H₂O) and polyhalite (K₂Ca₂Mg(SO₄)₄·2H₂O). These compounds are valuable fertilizer components in themselves, but the material’s porous nature helps absorb solutions of microelement fertilizers. Surprisingly, concentrated ammonium nitrate solutions transform the syngenite content of the porous fertilizer into ammonium calcium sulfate ((NH₄)₂Ca(SO₄)₂·2H₂O, koktaite). Koktaite is slightly soluble in water, thus the amount of ammonium ion released on the dissolution of koktaite depends on the amount of available water. Accordingly, ammonium ion release for plants can be increased with rain or irrigation, and koktaite is undissolved and does not decompose in drought situations. The pores (holes) of this sponge-like fertilizer product can be filled with different solutions containing other fertilizer components (phosphates, zinc, etc.) to adjust the composition of the requested fertilizer compositions for particular soils and plant production. The method allows the preparation of ammonium nitrate composite fertilizers containing metallic microelements, and various solid sponge-like composite materials with adjusted amounts of slowly releasing fertilizer components like syngenite and koktaite. Full article

A system combining gas-phase oxidation and liquid-phase collision absorption for removing NO from marine diesel engine exhaust was proposed. This method was the first to utilize different physical states of the same mixed solution to achieve both pre-oxidation and impingement reduction absorption of exhaust gases. During the pre-oxidation stage, a mixture of (NH₄)₂S₂O₈ and urea solution was atomized into a spray using an ultrasonic nebulizer to increase the contact area between the oxidant and the exhaust gas, thereby efficiently pre-oxidizing the exhaust gas in the gas phase. In the liquid-phase absorption stage, the (NH₄)₂S₂O₈ and urea solution was used in an impingement absorption process, which not only enhanced gas–liquid mass transfer efficiency but also effectively inhibited the formation of nitrates. Experimental results showed that, without increasing the amount of absorbent used, the maximum NO removal efficiency of this method reached 97% (temperature, 343 K; (NH₄)₂S₂O₈ concentration, 0.1 mol/L; urea concentration, 1.5 mol/L; NO concentration, 1000 ppm; pH, 7; impinging stream velocity, 15 m/s), compared to 72% using the conventional liquid-phase oxidation absorption method. Additionally, this method required only the addition of a nebulizer and two opposing nozzles to the existing desulfurization tower to achieve simultaneous removal of sulfur and nitrogen oxides from the exhaust gas, with low retrofitting costs making it favorable for practical engineering applications. Full article

Composting is one of the best organic waste management techniques, with zero waste; however, it generates environmental impacts. The objective of this study was to evaluate the emission of NH₃, N₂O, CO₂, and CH₄ from the composting of olive, elderberry, and grape agro-food waste. The experiment was carried out using reactors receiving straw as control and three treatments receiving mixtures of straw and olive, elderberry, or grape wastes. The gas emissions were measured for 150 days, and the composition of the mixtures and composts was determined. The results showed NH₃ and CH₄ emissions were reduced by 48% and 29% by the Olive and Elderberry treatments, while only NH₃ loss was reduced by 24% by the Grape treatment. Nitrous oxide, CO₂, and GWP emissions were reduced by 46%, 32%, and 34% by the Olive treatment, while these losses were not reduced by the Elderberry or Grape treatments. It can be concluded olive waste can effectively reduce NH₃ and GWP, while elderberry and grape wastes are also effective in reducing NH₃, but not GWP. Thus, the addition of agro-food waste appears to be a promising mitigation strategy to reduce gaseous losses from the composting process. Full article

Since photocatalytic reactions are surface reactions, enhancing gas movement around the photocatalyst could improve photocatalytic CO₂ reduction performance. A new approach using black body material to enhance the gas movement around the photocatalyst based on the natural thermosiphon movement of gases around a photocatalyst has been proposed and confirmed experimentally, but the heat-transfer mechanism of the phenomena has not yet been clarified. The aim of this study is to clarify the corresponding heat-transfer mechanism. This study calculated the temperature of the CO₂/NH₃ gas mixture around a P₄O₁₀/TiO₂ photocatalyst using the heat-transfer formula. No difference was found between the temperature increase (T_g) from the temperature at the beginning of the CO₂ reduction experiment (T_ini) and the temperature of the CO₂/NH₃ gas mixture measured experimentally via thermocouple (T_e) under the following illumination conditions: a Xe lamp with visible light (VIS) + infrared light (IR) and IR only. The heat-transfer model proposed in this study predicts T_g well under illumination from a Xe lamp with VIS + IR as well as under IR illumination only. On the other hand, the difference found between T_g and T_e was as large as 10 °C under illumination from a Xe lamp with ultraviolet light (UV) + VIS + IR. Full article

The evolution of the early atmosphere was driven by changes in its chemical composition, which involved the formation of some critical gases. In this study, we demonstrate that nitrous oxide (N₂O) can be produced from Miller’s early atmosphere (a mixture of CH₄, NH₃, H₂, and H₂O) by way of photocatalysis. Both NH₃ and H₂O were indispensable for the production of N₂O by photocatalysis. Different conditions related to seawater and reaction temperature are also explored. N₂O has a strong greenhouse gas effect, which is more able to warm the Earth than other gases and offers a reasonable explanation for the faint young Sun paradox on the early Earth. Moreover, the decomposition of N₂O into N₂ and O₂ can be boosted by soft irradiation, providing a possible and important origin of atmospheric O₂ and N₂. The occurrence of O₂ propelled the evolution of the atmosphere from being fundamentally reducing to oxidizing. This work describes a possible vital contribution of photocatalysis to the evolution of the early atmosphere. Full article

We report on the use of quartz-enhanced photoacoustic spectroscopy (QEPAS) for multi-gas detection. Photoacoustic (PA) spectra of mixtures of water (H${}_2$O), ammonia (NH${}_3$), and methane (CH${}_4$) were measured in the mid-infrared (MIR) wavelength range using a mid-infrared (MIR) optical parametric oscillator (OPO) light source. Highly overlapping absorption spectra are a common challenge for gas spectroscopy. To mitigate this, we used a partial least-squares regression (PLS) method to estimate the mixing ratio and concentrations of the individual gasses. The concentration range explored in the analysis varies from a few parts per million (ppm) to thousands of ppm. Spectra obtained from HITRAN and experimental single-molecule reference spectra of each of the molecular species were acquired and used as training data sets. These spectra were used to generate simulated spectra of the gas mixtures (linear combinations of the reference spectra). Here, in this proof-of-concept experiment, we demonstrate that after an absolute calibration of the QEPAS cell, the PLS analyses could be used to determine concentrations of single molecular species with a relative accuracy within a few % for mixtures of H${}_2$O, NH${}_3$, and CH${}_4$ and with an absolute sensitivity of approximately 300 (±50) ppm/V, 50 (±5) ppm/V, and 5 (±2) ppm/V for water, ammonia, and methane, respectively. This demonstrates that QEPAS assisted by PLS is a powerful approach to estimate concentrations of individual gas components with considerable spectral overlap, which is a typical scenario for real-life adoptions and applications. Full article

The results of sustainable and selective synthesis of glycerol carbonate (GC) from urea and glycerol under ambient pressure using carbon-fiber-supported metal oxide catalysts are reported. Carbon fibers (CF) were prepared via a catalytic chemical vapor deposition method (CCVD) using Ni as a catalyst and liquefied petroleum gas (LPG) as a cheap carbon source. Supported metal oxide catalysts were obtained by an incipient wetness impregnation technique using Zn, Ba, Cr, and Mg nitrates. Finally, the samples were pyrolyzed and oxidized in an air flow. The obtained catalysts (10%Me_xO_y/CF_ox) were tested in the reaction of urea glycerolysis at 140 °C for 6 h under atmospheric pressure, using an equimolar ratio of reagents and an inert gas flow for NH₃ removal. Under the applied conditions, all of the prepared catalysts increased the glycerol conversion and glycerol carbonate yield compared to the blank test, and the best catalytic performance was shown by the CF_ox-supported ZnO and MgO systems. Screening of the reaction conditions was carried out by applying ZnO/CF_ox as a catalyst and considering the effect of reaction temperature, molar ratio of reagents, and the mode of the inert gas flow through the reactor on the catalytic process. Finally, a maximum yield of GC of about 40%, together with a selectivity to glycerol carbonate of ~100%, was obtained within 6 h of reaction at 140 °C using a glycerol-to-urea molar ratio of 1:1 while flowing Ar through the reaction mixture. Furthermore, a positive heterogeneous catalytic effect of the CF_ox support on the process was noticed. Full article

Toxic industrial chemicals (TICs), when accidentally released into the workplace or environment, often form a gaseous mixture that complicates detection and mitigation measures. However, most of the existing gas sensors are unsuitable for detecting such mixtures. In this study, we demonstrated the detection and identification of gaseous mixtures of TICs using a chemiresistor array of single-walled carbon nanotubes (SWCNTs). The array consists of three SWCNT chemiresistors coated with different molecular/ionic species, achieving a limit of detection (LOD) of 2.2 ppb for ammonia (NH₃), 820 ppb for sulfur dioxide (SO₂), and 2.4 ppm for ethylene oxide (EtO). By fitting the concentration-dependent sensor responses to an adsorption isotherm, we extracted parameters that characterize each analyte-coating combination, including the proportionality and equilibrium constants for adsorption. Principal component analysis confirmed that the sensor array detected and identified mixtures of two TIC gases: NH₃/SO₂, NH₃/EtO, and SO₂/EtO. Exposing the sensor array to three TIC mixtures with various EtO/SO₂ ratios at a fixed NH₃ concentration showed an excellent correlation between the sensor response and the mixture composition. Additionally, we proposed concentration ranges within which the sensor array can effectively detect the gaseous mixtures. Being highly sensitive and capable of analyzing both individual and mixed TICs, our gas sensor array has great potential for monitoring the safety and environmental effects of industrial chemical processes. Full article

Novel yttrium-doped CeO₂, MnO_x, and CeMnO_x composites are investigated as catalysts for low-temperature NH₃-SCR. The study involves the preparation of unmodified oxide supports using a citrate method followed by modification with Y (2 wt.%) using two approaches, including the one-pot citrate method and incipient wetness impregnation of undoped oxides. The NH₃-SCR reaction is studied in a fixed-bed quartz reactor to test the ability of the prepared catalysts in NO reduction. The gas reaction mixture consists of 800 ppm NO, 800 ppm NH₃, 10 vol.% O₂, and He as a balance gas at a WHSV of 25,000 mL g⁻¹ h⁻¹. The results indicate that undoped CeMnO_x mixed oxide exhibits significantly higher deNO_x performance compared with undoped and Y-doped MnO_x and CeO₂ catalysts. Indeed, yttrium presence in CeMnO_x promotes the competitive NH₃-SCO reaction, reducing the amount of NH₃ available for NO reduction and lowering the catalyst activity. Furthermore, the physical-chemical properties of the prepared catalysts are studied using nitrogen adsorption/desorption, XRD, Raman spectroscopy, temperature-programmed reduction with hydrogen, and temperature-programmed desorption of ammonia. This study presents a promising approach to enhancing the performance of NH₃-SCR catalysts at low temperatures that can have significant implications for reducing NO emissions. Full article

Certain molecules act as biomarkers in exhaled breath or outgassing vapors of biological systems. Specifically, ammonia (NH₃) can serve as a tracer for food spoilage as well as a breath marker for several diseases. H₂ gas in the exhaled breath can be associated with gastric disorders. This initiates an increasing demand for small and reliable devices with high sensitivity capable of detecting such molecules. Metal-oxide gas sensors present an excellent tradeoff, e.g., compared to expensive and large gas chromatographs for this purpose. However, selective identification of NH₃ at the parts-per-million (ppm) level as well as detection of multiple gases in gas mixtures with one sensor remain a challenge. In this work, a new two-in-one sensor for NH₃ and H₂ detection is presented, which provides stable, precise, and very selective properties for the tracking of these vapors at low concentrations. The fabricated 15 nm TiO₂ gas sensors, which were annealed at 610 °C, formed two crystal phases, namely anatase and rutile, and afterwards were covered with a thin 25 nm PV4D4 polymer nanolayer via initiated chemical vapor deposition (iCVD) and showed precise NH₃ response at room temperature and exclusive H₂ detection at elevated operating temperatures. This enables new possibilities in application fields such as biomedical diagnosis, biosensors, and the development of non-invasive technology. Full article

This review paper illustrates the recommended monitoring technologies for the detection of various greenhouse gaseous emissions for solid waste thermochemical reactions, including incineration, pyrolysis, and gasification. The illustrated gas analyzers are based on the absorption principle, which continuously measures the physicochemical properties of gaseous mixtures, including oxygen, carbon dioxide, carbon monoxide, hydrogen, and methane, during thermochemical reactions. This paper illustrates the recommended gas analyzers and process control tools for different thermochemical reactions and aims to recommend equipment to increase the sensitivity, linearity, and dynamics of various thermochemical reactions. The equipment achieves new levels of on-location, real-time analytical capability using FTIR analysis. The environmental assessment study includes inventory analysis, impact analysis, and sensitivity analysis to compare the mentioned solid waste chemical recycling methods in terms of greenhouse gaseous emissions, thermal efficiency, electrical efficiency, and sensitivity analysis. The environmental impact assessment compares each technology in terms of greenhouse gaseous emissions, including CO₂, NO_x, NH₃, N₂O, CO, CH₄, heat, and electricity generation. The conducted environmental assessment compares the mentioned technologies through 15 different emission-related impact categories, including climate change impact, ecosystem quality, and resource depletion. The continuously monitored process streams assure the online monitoring of gaseous products of thermochemical processes that enhance the quality of the end products and reduce undesired products, such as tar and char. This state-of-the-art monitoring and process control framework provides recommended analytical equipment and monitoring tools for different thermochemical reactions to optimize process parameters and reduce greenhouse gaseous emissions and undesired products. Full article