Simplified design of steady-state recycling chromatography under ideal and nonideal conditions

In a recent contribution a design method for steady-state recycling chromatography in the so-called mixed-recycle mode (MR-SSR) has been proposed by Sainio and Kaspereit (2009). The method holds under ideal, dispersion-free conditions for chromatographic systems with competitive Langmuir adsorption isotherms. Here this approach is extended to practically relevant nonideal conditions with significant dispersive effects and convex-upward adsorption isotherms in general. The developed shortcut design method allows designing MR-SSR processes based on a simple procedure applied to a single conventional chromatogram. The method is validated experimentally for the separation of two cycloketones on a polymeric stationary phase. The performance of the MR-SSR process is compared to batch chromatography by means of a simulation study.     

Mild steel green inhibition by Ficus carica leaves extract under practical field conditions

Various electrochemical techniques were employed to study the effectiveness of aqueous Ficus carica (Fig. tree) leaves extract as green corrosion inhibitor for mild steel under field conditions containing 3.5% sodium chloride solution saturated with carbon dioxide. Optimum inhibition efficiency of 90% was obtained using 50 mg/L of inhibitor in the temperature range of 25–40 °C. The mode of action of Ficus carica leave extract as revealed by Polarization studies was shown to act as a mixed inhibitor. The adsorption isotherm of the adsorption of Ficus carica leaves extract on the steel surface was found to follow Langmuir adsorption isotherm. In order to assess the individual contribution of the different constituents of the extract theoretically, the adsorption of the four major organic constituents of Ficus carica leave extract on mild steel were modelled using density functional theory and quench molecular dynamic simulations. Among the four major Ficus carica leaves extract constituent investigated, Caffeoylmalic acid was found to make the most contribution to the overall inhibition action of Ficus carica leaves extract.     

The effect of delaying autumn incorporation of green manure crop on N mineralization and spring wheat (Triticum aestivum L.) performance

The use of legumes as green manuring crops does involve a potential riskof N leaching losses over the winter period. The susceptibility of cropresidue-derived N to losses and the pre-crop value of a green manuring crop canbe manipulated by proper timing of incorporation into soil. In this study,mineralization of C and N was investigated in a range of low temperatures,including thawing and freezing, that are characteristic to autumn green manureincorporation and its decomposition. The pre-crop effect of green manuring wasfurther tested with spring wheat under field conditions. We hypothesized thatdelaying green manure incorporation in the autumn would reduce the risk of Nlosses from the field and maximize the N transfer to a successive spring wheatcrop. To test the hypothesis, N mineralization was followed in alaboratory experiment where red clover (Trifoliumpratense L.) shoots were incubated at 4–8 °Cfor 40–80 days to simulate early autumn, delayed autumn and late autumnincorporation of a green manuring crop, followed by an incubation at–2 °C or at –2 °C to+4 °C for 25 days to simulate winter conditions. In asimultaneous field experiment, we measured the effect ofdelayed autumn incorporation of common vetch (Vicia sativaL.) green fallow on spring wheat performance. In the laboratoryexperiment, significant N mineralization during incubation wasdetected when simulating both early autumn and delayed autumn incorporation. Incontrast, no net N mineralization was detected when simulating lateincorporation. In the field experiment, the N supply fromsoil to spring wheat was higher in the late and delayed incorporationtreatmentsthan in early or spring incorporation of green manure. Late incorporationalso produced most wheat grain. We conclude that different amounts of N becomeavailable to wheat, depending on the time of incorporation of green manureresidues in soil. This difference is due to temperature. Late or delayedincorporation of green manure residues has the potential to reduce thesusceptibility of mineral N to leaching and yields more N available to asubsequent crop.     

Effect of green manure on the yield,N uptake and floodwater properties of a flooded rice,wheat rotation receiving15N urea on a highly permeable soil

Field studies were conducted for two years on a rapidly percolating loamy sand (Typic Ustochrept) to evaluate the effect of green manure (GM) on the yield,¹⁵N recovery from urea applied to flooded rice, the potential for ammonia loss and uptake of residual fertilizer N by succeeding crops. The GM crop ofSesbania aculeata was grownin situ and incorporated one day before transplanting rice. Urea was broadcast in 0.05 m deep floodwater, and incorporated with a harrow. Green manure significantly increased the yield and N uptake by rice and substituted for a minimum of 60 kg fertilizer N ha^–1. The recovery of fertilizer N as indicated by¹⁵N recovery was higher in the GM + urea treatments. The grain yield and N uptake by succeeding wheat in the rotation was slightly higher with GM. The recovery of residual fertilizer N as indicated by the¹⁵N recovery in the second, third and fourth crops of wheat, rice and wheat was only 3, 1 and 1 per cent of the urea fertilizer applied to the preceding rice crop. Floodwater chemistry parameters showed that the combined use of the GM and 40 kg N ha^–1 as urea applied at transplanting resulted in a comparatively higher potential for NH₃ loss immediately after fertilizer application. The actual ammonia loss as suggested by the¹⁵N recoveries in the rice crop, however, did not appear to be appreciably larger in the GM treatment. It appeared the ammonia loss was restricted by low ammoniacal-N concentration maintained in the floodwater after 2 to 3 days of fertilizer application.     

Efficient three-component Gewald reactions under Et3N/H2O conditions

In a medium consisting of triethylamine and water, α-methylene ketones undergo room temperature Gewald reactions with elemental sulfur and ethyl cyanoacetate (or malononitrile) to yield 2-aminothiophene derivatives efficiently within short time periods. Because of the high polarity of the medium, products precipitate in the reaction mixtures spontaneously. This makes isolation of the products easy by simple filtration and avoids cumbersome chromatographic separations. Mechanistic studies suggest that the reactions proceed via a Knoevenagel condensation pathway.     

Fluorine doped zinc oxide nanowires: Enhanced photocatalysts degrade malachite green dye under visible light conditions

Enhanced visible-light absorption of 4 at% fluorine (F) doped zinc oxide (ZnO) nanowires (F:ZnO) produced via a hydrothermal method with 15 M sodium hydroxide (NaOH) is explored with various characterization techniques: XRD, TEM, UV–vis spectra, Pl spectra, XPS, and surface area analysis. Moreover, photocatalytic performance of as-prepared samples is studied via degradation of malachite green dye under visible light irradiation. Finally, the photocatalyst’s optimal amount to use is determined as well as its recyclability. Results show that band gaps of ZnO nanostructures depend on NaOH concentration, doping 15 M NaOH resultant ZnO nanowires with 4 at% F further narrows the band gap, F:ZnO nanowires perform 1.6 times better than the pure ZnO nanowires in malachite green dye (MG) degradation tests, overloading the solution with the photocatalyst actually hinders degradation performance, and the F:ZnO photocatalyst remains a robust performer even after five cycles.     

Platinum/zinc oxide nanoparticles: Enhanced photocatalysts degrade malachite green dye under visible light conditions

Zinc oxide nanoparticles (ZnO) were prepared via a sol–gel method, and a photo-assisted deposition method was used to prepare platinum on zinc oxide nanoparticles (Pt/ZnO). Several techniques were used to characterize these enhanced photocatalysts: XRD, TEM, UV–vis spectra, PL spectra, XPS, and BET surface area analysis. As-prepared samples’ photocatalytic performances were studied via degradation of malachite green dye under various visible-light-only irradiation scenarios. Results demonstrated the following: platinum (Pt) was well dispersed on and in ZnO's surfaces and pores; as such, Pt/ZnO had less surface area than pure ZnO due to pore blockage; however, advantages gained from enhanced electron-hole separation and decreased band gap width more than made up for this negative effect; moreover, Pt/ZnO prepared with 0.3 wt% Pt exhibited the lowest band gap and the highest photocatalytic activity of the various samples with a solids loading of 0.8 g/l; finally, such samples were recyclable, i.e., photocatalytic performance remained stable even after five uses.     

Two-dimensional Fe-TPPHZ nanosheets for electrohydrogenation of N2 to NH3 under ambient conditions

Journal of Applied Electrochemistry - The design of high-performance and low-cost catalysts for mild electrocatalytic nitrogen reduction reaction (NRR) is particularly desirable and remains greatly...     

Effect of green manure on the incidence of cyanogenic Pseudomonas strains in hop garden soils

Incidence of cyanogenic Pseudomonas strains in hop garden soils in relation to the kind of fertilization was studied. Incidence differed with respect to the fertilization treatment and the age of the plantation. Amendment of soil with rye and with white mustard as green manures limited the number of cyanogenic Pseudomonas strains relative to farmyard manures and NPK fertilization. Among all fertilization treatments, cyanogenic Pseudomonas spp. strains had lowest populations in soils amended with white mustard.     

Biological nitrogen fixation in field-grown sorghum under different edaphoclimatic conditions is confirmed by N isotopic signatures

Nutrient Cycling in Agroecosystems - The association between sorghum and N2-fixing bacteria has been assessed only under limited conditions. We investigated biological nitrogen fixation (BNF) in...     

Turnover of15N ammonium sulfate with dicyandiamide under aerobic and anaerobic soil conditions

The influence of the nitrification inhibitor dicyandiamide (DCD) on the turnover of¹⁵N-labelled ammonium sulfate (AS) was investigated in two soils under aerobic and waterlogged conditions. Nitrification of ammonium sulfate was markedly inhibited by addition of DCD in both soils. Up to 45% of the supplied N was transformed into a non-extractable N form, which only slowly released nitrogen over 147 or 264 days. This immobilization was higher in the presence of DCD than without DCD. In all aerobic experiments, the recovery was 100% ± max. 2.4%, indicating that no gaseous losses of N occurred.If aerobic preincubation of 28 or 42 days was followed by water-logging with H₂O or a solution of glucose, considerable N losses occurred only in presence of the carbohydrate. DCD retarded nitrification and thus reduced losses by denitrification from 61 to 15%.DCD application resulted in an increased immobilization of labelled N into the non-exchangeable soil N fraction. This amounted to more than 50% of the applied N, compared to 39% without DCD.The late Dr. Klaus Vilsmeier, a very dedicated and talented young scientist, died before he was able to finish completely the revised version of this article. We will always keep him in our minds and kindly remember his kind personality as well as his sense of humour and justice. Prof. Dr. Heiner Goldbach on behalf of all members of the department.     

Laboratory and greenhouse assessment of plant availability of organic N in animal manure

Laboratory data (thermal fractionation, pepsin extraction, C:N_o ratio) of dung and manure were mutually compared and contrasted with plant-availability of organic N (N_o) as found in a greenhouse experiment according to the double-pot technique. Two types of fresh cow dung (one with a relatively wide and the other with a relatively narrow C:N_o ratio) and four types of manure (from poultry, sheep, pigs and cow) were compared with ammonium nitrate as chemical reference fertilizer. Relative effectiveness of organic N (RE_o) was used as characteristic; it was calculated as the fraction of organic N that has the same availability to plants as inorganic N. RE_o for poultry and sheep manure could not be assessed, probably because of NH₃ volatilization causing direct damage to plants and N losses. RE_o values decreased in the order: dung with narrow C:N_o > dung with wide C:N_o > pig manure > cow manure. Thermal fractionation did not provide a suitable index of plant-availability of organic N. Pepsin extracted organic N gave a positive, and C:N_o ratio a negative relationship with RE_o. Also between pepsin extracted organic N and C:N_o ratio a negative relationship was found. As C:N_o ratio is relatively easy to determine, it is considered the most practical laboratory index for plant availability of organic N in animal manures low in ammonia. When using the double-pot technique, application rates of manure types high in ammonia should be restricted.     

Recovery of 15N labeled wheat residue and residual effects of N fertilization in a wheat–wheat cropping system under Mediterranean conditions

A field study was conducted in arid-Saharan Morocco to assess the fate of fertilizer N in a wheat (Triticum durum var. Karim)–wheat cropping sequence. Therefore, 85 kg N ha^–1 labeled with 9.764 atom % excess ¹⁵N was applied in a three-split application. The fertilizer N recovery by the wheat in the first year was 33.1%. At harvest, 64.8% of fertilizer N was found in the 0–80 cm profile as residual fertilizer-derived N. 2.1% of the applied N could not be accounted for in the season 1996/1997. The recovery of the residual labeled fertilizer N by the subsequent wheat crop was 6.4% for the treatment without residue incorporation and 7.4% for the treatment with residue incorporation. The possible reason for this low plant recovery was immobilization of the fertilizer N. The total recovery of fertilizer N over the two growing seasons was 82.3% and 86.1% for the treatment without and with residue incorporation, respectively. The not recovered N after the second cropping season was 15.6% and 11.8% for the treatment without and with residue incorporation, respectively. The loss of labeled N by the soil–plant system was not due to leaching but to denitrification and volatilization. In the treatment (N+*R) with labeled residue incorporation, the percentage of N recovery by plant was 16.2, indicating the mineralisation of the residue applied.     

Emissions of NH3, N2O and CH4 from dairy cows housed in a farmyard manure tying stall (housing, manure storage, manure spreading)

Emission measurements from dairy cows housed in a tying stall were carried out with the aim of finding factors that influence the amount of emissions and means to reduce emissions. All sectors of animal husbandry were investigated. This enabled calculations of emissions for the whole management system including housing, storage and spreading of manure. Emissions during aerobic composting and anaerobic stacking of farmyard manure were compared. NH₃ and N₂O emissions from tying stalls for dairy cows are low (5.8 g NH₃ LU⁻¹ d⁻¹, 619.2 mg N₂O LU⁻¹ d⁻¹). Methane emissions from the animal housing are mainly caused by enteric fermentation. During storage and after spreading of farmyard manure substantial differences concerning NH₃, N₂O and CH₄ emissions were observed with composted and anaerobically stacked farmyard manure. The compost emitted more NH₃ than the anaerobically stacked farmyard manure. About one third of the NH₃ emissions from the anaerobically stacked farmyard manure occurred after spreading. Total N losses were at a low level with both storage systems. Greenhouse gas emissions (N₂O and CH₄) were much higher from the anaerobically stacked farmyard manure than from the composted one. As these are ecologically harmful gases, they have to be considered when judging the form of manure treatment. This revised version was published online in August 2006 with corrections to the Cover Date.     

A novel and green method for polycondensation reaction of 4-substituted phenylurazoles with different diisocyanates under solvent-free conditions

In this investigation, a new method for step-growth polymerization reactions of 4-phenylurazole ( PHU ) and 4-(4-methoxyphenyl)urazole ( MPU ) with various diisocyanates were developed under solvent-free conditions. The reaction of these monomers with hexamethylene diisocyanate ( HMDI ), isophorone diisocyanate ( IPDI ), and tolulyene-2,4-diisocyanate ( TDI ) were performed in the presence or absence of dibutyltin dilaurate ( DBTDL ) as a catalyst. The results of polymerization revealed that DBTDL did not have considerable effect on the polymerization process. The resulting polyureas showed good yields and moderate inherent viscosities ranging of 0.17–0.30 dL/g in N,N-dimethylformamide (DMF) at 25°C. They are soluble in most polar organic solvents. All of the above polymers were characterized by ¹H-NMR, FTIR spectroscopy, and thermogravimetric analysis (TGA). This method was compared with the polymerization reaction in N,N-dimethylacetamide as a solvent via solution polymerization. Under solvent-free conditions, higher yields and inherent viscosities were obtained. In addition, in this method we do not need to use any solvents and the polymerization reaction can be classified as a green and environmentally friendly method. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

An efficient,green and scale-up synthesis of amides from esters and amines catalyzed by Ru-MACHO catalyst under mild conditions

An efficient, green and scale-up synthesis of amides from esters and amines has been developed using Ru-MACHO as a readily available catalyst. A diverse range of amides were obtained in moderate to excellent yields (55–98%). Furthermore, when the scale of the amidation reaction was increased to 240.0 mmol, the desired amide still could be obtained in high yield (48.2 g of N-benzylbenzamide, 95%).     

Raising the productivity of smallholder farms under semi-arid conditions by use of small doses of manure and nitrogen: a case of participatory research

Participatory on-farm trials were conducted for three seasons to assess the benefits of small rates of manure and nitrogen fertilizer on maize grain yield in semi-arid Tsholotsho, Zimbabwe. Two farmer resource groups conducted trials based on available amounts of manure, 3 t ha⁻¹ (low resource group) and 6 t ha⁻¹ (high resource group). Maize yields varied between 0.15 t ha⁻¹ and 4.28 t ha⁻¹ and both absolute yields and response to manure were strongly related to rainfall received across seasons (P < 0.001). The first two seasons were dry while the third season received above average rainfall. Maize yields within the seasons were strongly related to N applied (R ² = 0.77 in season 1, and R ² = 0.88 and 0.83 in season 3) and other beneficial effects of manure, possibly availability of cations and P. In the 2001–2002 season (total rainfall 478 mm), application of 3 and 6 t ha⁻¹ of manure in combination with N fertilizer increased grain yield by about 0.14 and 0.18 t ha⁻¹, respectively. The trend was similar for the high resource group in 2002–2003 although the season was very dry (334 mm). In 2003–2004, with good rainfall (672 mm), grain yields were high even for the control plots (average 1.2 and 2.7 t ha⁻¹). Maize yields due to manure applications at 3 and 6 t ha⁻¹ were 1.96 and 3.44 t ha⁻¹, respectively. Application of 8.5 kg N ha⁻¹ increased yields to 2.5 t ha⁻¹ with 3 t ha⁻¹ of manure, and to 4.28 t ha⁻¹ with 6 t ha⁻¹ of manure. In this area farmers do not traditionally use either manure or fertilizer on their crops, but they actively participated in this research during three consecutive seasons and were positive about using the outcomes of the research in future. The results showed that there is potential to improve livelihoods of smallholder farmers through the use of small rates of manure and N under semi-arid conditions.     

Improving nutrient use efficiency from decomposing manure and millet yield under Plinthosols in Niger

To improve synchronicity between nutrients released from the decomposing manure with millet nutrient requirement under zaï technique, a 2-year field experiment was conducted at the International Crops Research Institute for the Semi-Arid Tropics Research Station, Sadoré, Niger. The treatments consisted of factorial combination of two rates of cattle manure (200 and 300 g per zaï hole), three periods of manure application (before planting, at planting and 15 days later) and two rates of mineral fertilizer [nitrogen (N), phosphorus (P) and potassium (K) 15–15–15] applied at 6 g per zaï hole and a control, without mineral fertilizer). Manure dry mass losses did not significantly differ among manure application periods in 2013. However, in 2014 the highest manure dry mass loss occurred when manure was applied before planting with 70% of manure applied being decomposed at millet maturity stage (115 days after litterbag installation) followed by manure applied at planting with almost 50% of dry mass losses. The quantities of N and P absorbed by millet at tillering stage represented, 61, 52 and 33% of N released and 15, 12 and 15% of P released at the same time when manure was applied before planting, at planting and 15 days after planting, respectively. Application of manure before planting increased on an average millet grain yield by 16 and 20% and N utilization efficiency by 25 and 31% compared to application of manure at planting and 15 days after planting respectively. Addition of mineral fertilizer induced a synergetic effect on millet grain yield (p = 0.002). Millet grain yields increased on average by 5, 17 and 57% when 6 g per zaï pit of NPK fertilizer were added to plots receiving manure application before planting, at planting and 15 days after planting, respectively. We conclude that application of manure prior to planting satisfies better millet nutrients demand, thereby increasing nutrient use efficiency and grain yield under zai pits.