An aggregated understanding of the influence of aqueous ammonia pretreatment on the physical deconstruction of cell walls in sugar beet pulp.

The underlying interplay between physicochemical property and enzymatic hydrolysis of cellulose still remains unclear. The impacts of matrix glycan composition of sugar beet pulp (SBP) on physical structure and saccharification efficiency were emphasized. The results showed that aqueous ammonia (AA) pretreatment could remove the non-cellulosic polysaccharides and destroy the linkage between the pectin and lignin. The cellulose supramolecule was changed significantly after AA pretreatment, in terms of the decline in hardness, gumminess, springiness, thickness and degree of polymerization. Furthermore, vascular cell was exposed and degraded. The highest reducing sugar yield of 355.06 mg/g was obtained from the pretreated SBP (80 °C) with enzyme loading of 30 U/g, which was 1.01 times higher than that of the untreated SBP. This research also supported the idea that recognizing and precisely removing the primary epitopes in cell walls might be an ideal strategy to accomplish the improved enzymatic hydrolysis through mild pretreatment.

Study on mutual harmless treatment of electrolytic manganese residue and red mud.

Electrolytic manganese residue (EMR) and red mud (RM) are solid waste by-products of the metal manganese and alumina industries, respectively. Under long-term open storage, ammonia nitrogen and soluble manganese ions in EMR and alkaline substances in RM severely pollute and harm the environment. In order to alleviate the pollution problem of EMR and RM. In this study, the alkaline substances in RM were used to treat ammonia nitrogen and soluble manganese ions in EMR. The results confirm the following suitable treatment conditions for the mutual treatment of EMR and RM: EMR-RM mass ratio = 1:1, liquid-solid ratio = 1.4:1, and stirring time = 320 min. Under these conditions, the elimination ratios of ammonia nitrogen (emitted in the form of ammonia gas) and soluble manganese ions (solidified in the form of Mn3.88O7(OH) and KMn8O16) are 85.87 and 86.63%, respectively. Moreover, the alkaline substances in RM are converted into neutral salts (Na2SO4 and Mg3O(CO3)2), achieving de-alkalinisation. The treatment method can also solidify the heavy metal ions-Cr3+, Cu2+, Ni2+, and Zn2+-present in the waste residue with leaching concentrations of 1.45 mg/L, 0.099 mg/L, 0.294 mg/L, and 0.449 mg/L, respectively. This satisfies the requirements of the Chinese standard GB5085.3-2007. In the mutual treatment of EMR and RM, the kinetics of ammonia nitrogen removal and manganese-ion solidification reactions are controlled via a combination of membrane diffusion and chemical reaction mechanisms.

Effective removal of ammonia from aqueous solution through struvite synthesis and breakpoint chlorination: Insights into the synergistic effects of the hybrid system.

The ever-growing contamination of surface water due to various catchment activities poses threats and stress to downstream water treatment entities. Specifically, the presence of ammonia, microbial contaminants, organic matter, and heavy metals has been an issue of paramount concern to water treatment entities since stringent regulatory frameworks require these pollutants to be removed prior to water consumption. Herein, a hybrid approach that integrates struvite crystallization (precipitation) and breakpoint chlorination (stripping) for the removal of ammonia from aqueous solution was evaluated. To fulfil the goals of this study, batch experimental studies were pursued through the adoption of the well-known one-factor-at-a-time (AFAAT) method, specifically the effects of time, concentration/dosage, and mixing speed. The fate of chemical species was underpinned using the state-of-the-art analytical instruments and accredited standard methods. Cryptocrystalline magnesium oxide nanoparticles (MgO-NPs) were used as the magnesium source while the high-test hypochlorite (HTH) was used as the source of chlorine. From the experimental results, the optimum conditions were observed to be, i.e., Stage 1 - struvite synthesis, 110 mg/L of Mg and P dosage (concentration), 150 rpm of mixing speed, 60 min of contact time, and lastly, 120 min of sedimentation while optimum condition for the breakpoint chlorination (Stage 2) were 30 min of mixing and 8:1 Cl2:NH3 weight ratio. Specifically, in Stage 1, i.e., MgO-NPs, the pH increased from 6.7 to ≥9.6, while the turbidity was reduced from 9.1 to ≤1.3 NTU. Mn removal efficacy attained ≥97.70% (reduced from 174 µg/L to 4 µg/L) and Fe attained ≥96.64% (reduced from 11 mg/L to 0.37 mg/L). Elevated pH also led to the deactivation of bacteria. In Stage 2, i.e. breakpoint chlorination, the product water was further polished by eliminating residual ammonia and TPC at 8:1 Cl2-NH3 weight ratio. Interestingly, ammonia was reduced from 6.51 to 2.1 mg/L in Stage 1 (67.74% removal) and then from 2.1 to 0.002 mg/L post breakpoint chlorination (99.96% removal), i.e., stage 2. Overall, synergistic and complementary effects of integrating struvite synthesis and breakpoint chlorination hold great promise for the removal of ammonia from aqueous solutions thus confirming that this technology could potentially be used to curtail the effects of ammonia in the receiving environments and drinking water.

Balancing acid and redox sites of phosphorylated CeO2 catalysts for NOx reduction: The promoting and inhibiting mechanism of phosphorus.

The role of phosphorus in metal oxide catalysts is still controversial. The precise tuning of the acidic and redox properties of metal oxide catalysts for the selective catalytic reduction in NOx using NH3 is also a great challenge. Herein, CeO2 catalysts with different degrees of phosphorylation were used to study the balance between the acidity and redox property by promoting and inhibiting effects of phosphorus. CeO2 catalysts phosphorylated with lower phosphorus content (5 wt%) exhibited superior NOx reduction performance with above 90% NOx conversion during 240-420 °C due to the balanced acidity and reducibility derived from the highest content of Brønsted acid sites on PO43- to adsorb NH3 and surface adsorbed oxygen species. Plenty of PO3- over CeO2 catalysts phosphorylated with the higher phosphorus content (≥ 10 wt%) significantly disrupted the balance between the acidity and the redox property due to the reduced acid/redox sites, which resulted in the less active NOx species. The mechanism of different structural phosphorus species (PO43- and PO3-) in promoting or inhibiting the NOx reduction over CeO2 catalysts was revealed. This work provides a novel method for qualitative and quantitative study of the relationship between acidity/redox property and activity of catalysts for NOx reduction.

Mechanochemical synthesis of alumina-based catalysts enriched with vanadia and lanthana for selective catalytic reduction of nitrogen oxides.

Novel alumina-based materials enriched with vanadia and lanthana were successfully synthesized via in situ modification using a mechanochemical method, and were applied in ammonia-induced selective catalytic reduction of nitrogen oxides (SCR process). The synthesis was optimized in terms of the ball milling time (3 or 5 h), vanadium content (0.5, 1 or 2 wt% in the final product), and lanthanum content (0.5 or 1 wt% in the final product). Vanadium (V) oxide was immobilized on an alumina support to provide catalytic activity, while lanthana was introduced to increase the affinity of nitrogen oxides and create more active adsorption sites. Mechanochemical synthesis successfully produced mesoporous materials with a large specific surface area of 279-337 m2/g and a wide electrokinetic potential range from 60 to (- 40) mV. Catalytic tests showed that the incorporation of vanadia resulted in a very large improvement in catalytic performance compared with pristine alumina, increasing its efficiency from 14 to 63% at 400 °C. The best SCR performance, a 75% nitrogen oxide conversion rate at a temperature of 450 °C, was obtained for alumina enriched with 2 and 0.5 wt% of vanadium and lanthanum, respectively, which may be considered as a promising result.

Effect of incremental proportions of Desmanthus spp. in isonitrogenous forage diets on growth performance, rumen fermentation and plasma metabolites of pen-fed growing Brahman, Charbray and Droughtmaster crossbred beef steers.

Desmanthus (Desmanthus spp.), a tropically adapted pasture legume, is highly productive and has the potential to reduce methane emissions in beef cattle. However, liveweight gain response to desmanthus supplementation has been inconclusive in ruminants. This study aimed to evaluate weight gain, rumen fermentation and plasma metabolites of Australian tropical beef cattle in response to supplementation with incremental levels of desmanthus forage legume in isonitrogenous diets. Forty-eight Brahman, Charbray and Droughtmaster crossbred beef steers were pen-housed and fed a basal diet of Rhodes grass (Chloris gayana) hay supplemented with 0, 15, 30 or 45% freshly chopped desmanthus forage on dry matter basis, for 140 days. Varying levels of lucerne (Medicago sativa) hay were added in the 0, 15 and 30% diets to ensure that all diets were isonitrogenous with the 45% desmanthus diet. Data were analyzed using the Mixed Model procedures of SAS software. Results showed that the proportion of desmanthus in the diet had no significant effect on steer liveweight, rumen volatile fatty acids molar proportions and plasma metabolites (P ≥ 0.067). Total bilirubin ranged between 3.0 and 3.6 µmol/L for all the diet treatments (P = 0.67). All plasma metabolites measured were within the expected normal range reported for beef cattle. Rumen ammonia nitrogen content was above the 10 mg/dl threshold required to maintain effective rumen microbial activity and maximize voluntary feed intake in cattle fed low-quality tropical forages. The average daily weight gains averaged 0.5 to 0.6 kg/day (P = 0.13) and were within the range required to meet the target slaughter weight for prime beef markets within 2.5 years of age. These results indicate that desmanthus alone or mixed with other high-quality legume forages can be used to supplement grass-based diets to improve tropical beef cattle production in northern Australia with no adverse effect on cattle health.

The Effect of Modifiers on the Performance of Ni/CeO2 and Ni/La2O3 Catalysts in the Oxy-Steam Reforming of LNG.

This work interrogates for the first time the catalytic properties of various monometallic Ni catalysts in the oxy-steam reforming of LNG. Various research techniques, including X-ray diffraction (XRD), specific surface area and porosity analysis (BET method), scanning electron microscopy with X-ray microanalysis (SEM-EDS), temperature-programmed desorption of ammonia (TPD-NH3), temperature-programmed reduction (TPR-H2) and the FTIR method, were used to study their physicochemical properties. The mechanism of the oxy-steam reforming of LNG is also discussed in this paper. The high activity of monometallic catalysts supported on 5% La2O3-CeO2 and 5% ZrO2-CeO2 oxides in the studied process have been proven and explained on the basis of their acidity, specific surface area, sorption properties in relation to the reaction products, the crystallite size of the metallic nickel and their phase composition.

Mosquito Attractants.

Vector control and personal protection against anthropophilic mosquitoes mainly rely on the use of insecticides and repellents. The search for mosquito-attractive semiochemicals has been the subject of intense studies for decades, and new compounds or odor blends are regularly proposed as lures for odor-baited traps. We present a comprehensive and up-to-date review of all the studies that have evaluated the attractiveness of volatiles to mosquitoes, including individual chemical compounds, synthetic blends of compounds, or natural host or plant odors. A total of 388 studies were analysed, and our survey highlights the existence of 105 attractants (77 volatile compounds, 17 organism odors, and 11 synthetic blends) that have been proved effective in attracting one or several mosquito species. The exhaustive list of these attractants is presented in various tables, while the most common mosquito attractants - for which effective attractiveness has been demonstrated in numerous studies - are discussed throughout the text. The increasing knowledge on compounds attractive to mosquitoes may now serve as the basis for complementary vector control strategies, such as those involving lure-and-kill traps, or the development of mass trapping. This review also points out the necessity of further improving the search for new volatile attractants, such as new compound blends in specific ratios, considering that mosquito attraction to odors may vary over the life of the mosquito or among species. Finally, the use of mosquito attractants will undoubtedly have an increasingly important role to play in future integrated vector management programs.

Isolation and Characterization of Fungal Endophytes Isolated from Medicinal Plant Ephedra pachyclada as Plant Growth-Promoting.

Endophytic fungi are widely present in internal plant tissues and provide different benefits to their host. Medicinal plants have unexplored diversity of functional fungal association; therefore, this study aimed to isolate endophytic fungi associated with leaves of medicinal plants Ephedra pachyclada and evaluate their plant growth-promoting properties. Fifteen isolated fungal endophytes belonging to Ascomycota, with three different genera, Penicillium, Alternaria, and Aspergillus, were obtained from healthy leaves of E. pachyclada. These fungal endophytes have varied antimicrobial activity against human pathogenic microbes and produce ammonia and indole acetic acid (IAA), in addition to their enzymatic activity. The results showed that Penicillium commune EP-5 had a maximum IAA productivity of 192.1 ± 4.04 µg mL-1 in the presence of 5 µg mL-1 tryptophan. The fungal isolates of Penicillium crustosum EP-2, Penicillium chrysogenum EP-3, and Aspergillus flavus EP-14 exhibited variable efficiency for solubilizing phosphate salts. Five representative fungal endophytes of Penicillium crustosum EP-2, Penicillium commune EP-5, Penicillium caseifulvum EP-11, Alternaria tenuissima EP-13, and Aspergillus flavus EP-14 and their consortium were selected and applied as bioinoculant to maize plants. The results showed that Penicillium commune EP-5 increased root lengths from 15.8 ± 0.8 to 22.1 ± 0.6. Moreover, the vegetative growth features of inoculated maize plants improved more than the uninoculated ones.

Carbohydrate-based films containing pH-sensitive red barberry anthocyanins: Application as biodegradable smart food packaging materials.

A novel pH-sensitive colorimetric film was prepared based on immobilizing red barberry anthocyanins (RBAs) within composite chitin nanofiber (CNF) and methylcellulose (MC) matrices. The incorporation of CNFs and RBAs improved their mechanical properties, moisture resistance, and UV-vis screening properties. Moreover, the RBAs could be used as colorimetric indicators to detect food spoilage because they are sensitive to changes in pH and ammonia gas production. The RBA-halochromic indicator changed from reddish/crimson → pink → yellow with increasing pH, and from pink → yellow with increasing ammonia vapor concentration. Furthermore, the smart films possessed good antioxidant and antimicrobial activity owing to the presence of the RBAs and CNFs. Finally, the validity of the indicator to monitor the freshness/spoilage of a model food (fish) was demonstrated. Overall, this study shows that active/smart films can be assembled from food grade ingredients that can protect and monitor the freshness of products, like meat and fish.

Butyric Acid Generation by Clostridium tyrobutyricum from Low-Moisture Anhydrous Ammonia (LMAA) Pretreated Sweet Sorghum Bagasse.

Sweet sorghum bagasse (SSB) is an under-utilized feedstock for biochemical conversion to biofuels or high value chemicals. One such chemical that can be generated biochemically and applied to a wide array of industries from pharmaceuticals to the production of liquid transportation fuels is butyric acid. This work investigated cultivating the butyric acid producing strain Clostridium tyrobutyricum ATCC 25755 on low-moisture anhydrous ammonia (LMAA) pretreated SSB. Pretreated SSB hydrolysate was detoxified and supplemented with urea for shake flask batch fermentation to show that up to 11.4 g/L butyric acid could be produced with a selectivity of 87% compared to other organic acids. Bioreactor fermentation with pH control showed high biomass growth, but a similar output of 11.3 g/L butyric acid was achieved. However, the butyric acid productivity increased to 0.251 g/L∙hr with a butyric acid yield of 0.29 g/g sugar consumed. This butyric acid output represented an 83% theoretical yield. Further improvements in butyric acid titer and yield can be achieved by optimizing nutrient supplementation and incorporating fed-batch fermentation processing of pretreated SSB hydrolysate. Construction of ZGO:Sr NR- and ZGC@PDA NP-driven ratiometric aptasensor for CEA detection.

Black Tea Theaflavin Detoxifies Metabolic Toxins in the Intestinal Tract of Mice.

SCOPE: This study is to determine the in vivo efficacy of black tea theaflavin (TF) to detoxify two metabolic toxins, ammonia and methylglyoxal (MGO), in mice METHODS AND RESULTS: Under in vitro conditions, TF is able to react with ammonia, MGO, and hydrogen peroxide to produce its aminated, MGO conjugated, and oxidized products, respectively. In TF-treated mice, the aminated TF, the MGO conjugates of TF and aminated TF, and the oxidized TF are searched using LC-MS/MS. The results provide the first in vivo evidence that the unabsorbed TF is able to trap ammonia to form the aminated TF; furthermore, both TF and the aminated TF have the capacity to trap MGO to generate the corresponding mono-MGO conjugates. Moreover, TF is oxidized to dehydrotheaflavin, which underwent further amination in the gut. By exposing TF to germ-free (GF) mice and conventionalized mice (GF mice colonized with specific-pathogen-free microbiota), the gut microbiota is demonstrated to facilitate the amination and MGO conjugation of TF. CONCLUSION: TF has the capacity to remove the endogenous metabolic toxins through oxidation, amination, and MGO conjugation in the intestinal tract, which can potentially explain why TF still generates in vivo efficacy while showing a poor systematic bioavailability.

A non-perturbative pairwise-additive analysis of charge transfer contributions to intermolecular interaction energies.

Energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs) decomposes the interaction energy between molecules into physically interpretable components like geometry distortion, frozen interactions, polarization, and charge transfer (CT, also sometimes called charge delocalization) interactions. In this work, a numerically exact scheme to decompose the CT interaction energy into pairwise additive terms is introduced for the ALMO-EDA using density functional theory. Unlike perturbative pairwise charge-decomposition analysis, the new approach does not break down for strongly interacting systems, or show significant exchange-correlation functional dependence in the decomposed energy components. Both the energy lowering and the charge flow associated with CT can be decomposed. Complementary occupied-virtual orbital pairs (COVPs) that capture the dominant donor and acceptor CT orbitals are obtained for the new decomposition. It is applied to systems with different types of interactions including DNA base-pairs, borane-ammonia adducts, and transition metal hexacarbonyls. While consistent with most existing understanding of the nature of CT in these systems, the results also reveal some new insights into the origin of trends in donor-acceptor interactions.

Comparison of Chemical Composition between Kuromoji (Lindera umbellata) Essential Oil and Hydrosol and Determination of the Deodorizing Effect.

Kuromoji (Lindera umbellata) is a tree that grows throughout Japan. The components of kuromoji essential oil have antitumor and aromatherapy effects. However, the composition of the hydrosol, obtained as a by-product of the essential oil process, is unknown. Furthermore, it is unknown whether kuromoji essential oil has a deodorizing effect. Therefore, the purpose of the current study was to compare the chemical composition of kuromoji essential oil and hydrosol, as well as evaluate the deodorizing effect of the former. The chemical composition of samples was evaluated using gas chromatography-mass spectrometry (GC-MS). Additionally, the deodorizing effect of Kuromoji essential oil was investigated with the detector tube method using ammonia, hydrogen sulfide, methyl mercaptan, and isovaleric acid. Linalool was the most abundant component in both the essential oil and hydrosol; however, its proportion was higher in the hydrosol (57.5%) than in the essential oil (42.8%). The hydrosol contained fewer chemical components, but higher proportions of trans-geraniol and ethanol. Moreover, the essential oil eliminated 50% of ammonia and 97.6% or more of isovaleric acid. Interestingly, linalool was soluble in the hydrosol and did not irritate the skin. This suggests that the hydrosol may be an effective foot care product.

Advanced nitrogen and phosphorus removal from municipal wastewater via simultaneous enhanced biological phosphorus removal and semi-nitritation (EBPR-SN) combined with anammox.

In this study, a novel laboratory-scale synchronous enhanced biological phosphorus removal and semi-nitritation (termed as EBPR-SN) combined with anammox process was put forward for achieving nutrient elimination from municipal wastewater at 27 ℃. This process consisted of two 10 L sequencing batch reactors (SBRs), i.e. EBPR-SN SBR followed by Anammox SBR. The EBPR-SN SBR was operated for 400 days with five periods and the Anammox SBR was operated starting on period IV. Eventually, for treating municipal wastewater containing low chemical oxygen demand/nitrogen (COD/N) of 3.2 (mg/mg), the EBPR-SN plus Anammox system performed advanced total inorganic nitrogen (TIN) and P removal, with TIN and P removal efficiencies of 81.4% and 94.3%, respectively. Further analysis suggested that the contributions of simultaneous partial nitrification denitrification, denitrification, and anammox to TIN removal were 15.0%, 45.0%, and 40.0%, respectively. The enriched phosphorus-accumulating organisms (PAOs) in the EBPR-SN SBR facilitated P removal. Besides, the EBPR-SN SBR achieved P removal and provided stable anammox substrates, suggesting a short sludge retention time (SRT 12 d) could achieve synergy between ammonia-oxidizing bacteria and PAOs. These results provided an alternative process for treating municipal wastewater with limited organics.

Formation of 3-hydroxypyridines by lipid oxidation products in the presence of ammonia and ammonia-producing compounds.

Pyridines are produced during food processing and are important flavor compounds. In spite of that, their formation pathways are still poorly understood, in particular those related to 3-hydroxypyridines. In an attempt to fill this gap, this study describes, for the first time, precursors and reaction pathways leading to 3-hydroxypyridine formation. 3-Hydroxypyridines are produced by reaction of lipid-derived reactive carbonyls and ammonia-producing compounds and were studied by using gas chromatography coupled to mass spectrometry. Their main precursors resulted to be 4,5-epoxy-2-alkenals and 2,4-alkadienals. 3-Hydroxypyridines were produced at temperatures higher than 100 °C, at slightly basic pH values, and with an activation energy of about 50 kJ/mol. A reaction pathway that explains their formation in the course of the lipid oxidation pathway is proposed. The role of lipid oxidation on the production of 3-hydroxypyridines was confirmed by studying their formation in oxidized linseed and menhaden oils heated in the presence of glutamine.

A novel method for the stabilization of soluble contaminants in electrolytic manganese residue: Using low-cost phosphogypsum leachate and magnesia/calcium oxide.

Electrolytic manganese residue (EMR) contains a large amount of NH4+-N and Mn2+ and can negatively impact the environment. A stabilization treatment of soluble contaminants in the EMR is necessary for its reuse and safe stacking. This study presents experimental results for the stabilization of NH4+-N and Mn2+ in the EMR using phosphogypsum leachate as a low-cost phosphate source and MgO/CaO (PLMC) process. The results demonstrated that the stabilization efficiency of NH4+-N and Mn2+ was 93.65% and 99.99%, respectively, under the following conditions: a phosphogypsum leachate dose of 1.5 mL g-1, an added MgO dose of 0.036 g g-1, an added CaO dose of 0.1 g g-1 and a reaction time of 2 h. The stabilization effect of the PLMC process was higher and more cost effective than that of using Na3PO4·12H2O and MgO/CaO. The concentration of NH4+-N and Mn2+ in the leaching liquor decreased to 80 mg L-1 and 0.5 mg L-1, respectively, after the stabilization under the optimum conditions. The stabilization characteristics indicated that NH4+-N was stabilized to form NH4MgPO4·6H2O (struvite) and that Mn2+ was stabilized to form Mn5(PO4)2(OH)4, Mn3(PO4)2·3H2O and Mn(OH)2. PO43--P, F-, and heavy metal ions of the phosphogypsum leachate were removed from the leaching liquor and stabilized in the treated EMR.

pH-Zone-refining counter-current chromatography for two new lipo-alkaloids separated from refined alkaline extraction of Kusnezoff monkshood root.

An efficient and refined method for the separation of six aconitine-type alkaloids from the alkaline prepared "Kusnezoff monkshood root" was established. It is the first study that two new lipo-alkaloids were successfully isolated from refined sample by pH-zone-refining counter-current chromatography rather than synthetic method. It was of interest that a great deal of lipo-alkaloids was produced in crude extract from the alkalization of "Kusnezoff monkshood root." A refined sample method was proposed to enrich two types of alkaloids by liquid-liquid extraction, i.e. lipo-alkaloids and monoester-diterpenoid alkaloids. The pH-zone-refining counter-current chromatography was performed with an optimized two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (3:5:4:5, v/v), where upper organic phase was added to 3 mmol/L triethylamine as a retainer and lower aqueous mobile phase was added to 3 mmol/L hydrochloric acid as an eluter. As a result, six aconitum alkaloids, including two lipo-alkaloids (8-lino-14-benzoylaconine, 8-pal-14-benzoylaconine), three monoester-diterpenoid alkaloids (14-benzoylmesaconine, 14-benzoylaconine, beyzoyldeoxyaconine), and one aconine alkaloid (neoline) were acquired from the plant at the same time. The anti-inflammatory activities of the two new lipo-alkaloids were compared to the six alkaloids in vitro, in cyclo-oxygen-ase-2 inhibition assays. The separation mechanism of six alkaloids by pH-zone-refining counter-current chromatography was illustrated.

Spectroscopic identification and catalytic relevance of NH4+ intermediates in selective NOx reduction over Cu-SSZ-13 zeolites.

Reduction of harmful nitrogen oxides (NOx) from diesel engine exhausts is one of the key challenges in environmental protection, and can be achieved by NH3-assisted selective catalytic reduction (NH3-SCR) using copper-exchanged chabazite zeolites (i.e. Cu-CHA, including Cu-SSZ-13 and Cu-SAPO-34) as catalysts. Understanding the redox chemistry of Cu-CHA in NH3-SCR catalysis is crucial for further improving the NOx reduction efficiency. Here, a series of Cu-SSZ-13 catalysts with different Cu ion exchange levels were prepared, thoroughly characterized by different techniques such as X-ray diffraction, diffuse reflectance ultraviolet-visible spectroscopy and temperature-programmed desorption using NH3 as a probe molecule, etc., and tested in NH3-SCR reactions under steady-state conditions. In situ studies by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), supplemented with density-functional theory calculations, provided solid evidence for the formation of ammonium ion (NH4+) intermediates resulting from the reduction of Cu2+ to Cu+ by co-adsorbed NH3 and NO molecules on Cu-SSZ-13. Catalytic relevance of the NH4+ intermediates, as demonstrated by an increase of NO conversion over Cu-SSZ-13 pre-treated in NH3/NO atmosphere, can be attributed to the formation of closely coupled Cu+/NH4+ pairs promoting the Cu+ re-oxidation and, consequently, the overall NH3-SCR process. This study thus paves a new route for improving the NH3-SCR efficiency over Cu-CHA zeolite catalyst.

Sewage sludge-derived hydrochar that inhibits ammonia volatilization, improves soil nitrogen retention and rice nitrogen utilization.

Hydrothermal carbonization (HTC) is a promising technique for treating sewage sludge. In this study, three sewage sludge-derived hydrochars produced with water (SSHW), 1 wt% magnesium citrate (SSHM) solution, and 1 wt% magnesium citrate mixed with 1 wt% sulfuric acid (SSHMS) solution were applied to columns of packed paddy soil. We evaluated the effects of these differently modified sewage sludge-hydrochars on ammonia volatilization, soil nitrogen (N) retention and rice growth. Results showed that compared to the control, SSHMS reduced the cumulative ammonia volatilization determined after three split application of N-fertilizer. SSHM and SSHMS both reduced the yield-scale ammonia volatilization by 20.3% and 41.2% respectively. Moreover, the addition of three sewage sludge-derived hydrochars increased soil ammonium-N retention after the first supplementary fertilization; however, after the second supplementary fertilization, only SSHMS addition significantly increased soil ammonium-N retention. Of the three hydrochars tested, SSHMS has the strongest effects on soil ammonium-N retention and inhibition of ammonium-N loss in floodwater. This was attributed to increased ammonium sorption driven by SSHMS's lower surface pH and porous diameter, larger adsorption porous volume and higher abundance of carboxyl functional groups. Additionally, the increased soil N retention increased grain N content and yield. Our results provide a novel method to valorize sewage sludge into a valuable fertilizer that if applied to paddy soil it can inhibit ammonia volatilization, N loss in floodwater, and promote N use efficiency by rice, with positive implications for sustainable rice production.