Subsoil <Superscript>15</Superscript>N-N<Subscript>2</Subscript>O Concentrations in a Sandy Soil Profile After Application of <Superscript>15</Superscript>N-fertilizer

Studies on emissions of nitrous oxide (N₂O) from agricultural soils mostly focus on fluxes between the soil and the atmosphere or are limited to the atmosphere in the topsoil. However, in soils with shallow water tables, significant N₂O formation may occur closer to the groundwater. The aims of this study were (i) to determine the importance of subsoil N₂O formation in a sandy soil; and (ii) to obtain a quantitative insight in the contribution of subsoil N₂O to the overall losses of N₂O to the environment. We applied ¹⁵N labeled fertilizer at a rate of 5.22 kg ¹⁵N ha⁻¹; 50% as Ca(NO₃)₂ and 50% as NH₄Cl, on a mesic typic Haplaquod seeded with potatoes (Solanum tuberosum L.), and traced soil N₂O concentrations and fluxes over a one-year period. Throughout the year, total N₂O and the amount of ¹⁵N recovered in soil N₂O were highest in the subsoil, with a maximum concentration at 48 cm depth in mid-February of 19900 μl m⁻³ and 24 μg ¹⁵N m⁻³, respectively. The maximum concentration coincided with the highest water-filled pore space of 71%. The cumulative flux of N₂O was 446 g N₂O-N ha⁻¹, the recovery of ¹⁵N in this flux was 0.06%. During the summer, maximum fluxes followed high soil N₂O concentrations. During winter, no such relation was found. We concluded that the formation of N₂O was the highest in the subsoil, largely controlled by water-filled pore space rather than NO₃⁻ concentration or temperature. Although high subsoil N₂O concentrations did not lead to high surface fluxes of N₂O in the winter, artificial draining may lead to high indirect N₂O emissions through supersaturated drainage water.     

Recovery of mineral fertiliser N and slurry N in continuous silage maize using the <Superscript>15</Superscript>N and difference methods

The stable isotope technique and the difference method are common approaches for estimating fertiliser N uptake efficiency. Both methods, however, have limitations and their suitability may depend on N management and environmental conditions. A field experiment was conducted on a humus sandy soil in northern Germany to estimate fertiliser N uptake efficiency of silage maize in the year of application (Zea mays L.) by the stable isotope and the difference method as influenced by the type of N fertiliser (mineral vs. cattle slurry), the application mode (separate or combined application), and N rate. Seven N treatments were included (0, 50, 100 and 150 kg mineral N ha⁻¹; 20, 40 m3 cattle slurry ha⁻¹; 50 kg mineral N ha⁻¹ plus 40 m3 slurry ha⁻¹), where either mineral N or slurry N was labelled, and mineral N was split into two dressings. In addition, 4.1 kg ha⁻¹ labelled mineral N was incorporated into otherwise unlabelled treatments (0, 20, 40 m3 ha⁻¹, and 50 kg mineral N ha⁻¹ plus 40 m3 ha⁻¹) to estimate N uptake from the upper soil layer. Uptake of ¹⁵N was followed in leaves, stalk, ear, and the whole crop. Fertiliser N uptake efficiency (FNUE_15N) of mineral fertiliser N obtained by the isotope technique ranged between 51 and 61%. Recovered fertiliser N was mainly found in the ear, while less labelled N remained in leaves and the stalk. The nitrogen rate tended to increase the amount of recovered N, but the effect was not consistent among plant parts and the whole crop. Plant N uptake from non-fertiliser N was found to increase N input up to 100 kg N ha⁻¹. Nitrogen recoveries of the two mineral N dressings were similar for the different plant parts as well as for the whole crop. Fertiliser N uptake efficiency (FNUE_diff) of mineral N estimated by the difference method resulted in substantially higher values compared to FNUE_15N, varying between 56 and 98%. More N was taken up from the upper soil layer with increasing N supply, which is regarded as a major error source of the difference method. Slurry N was taken up less efficient in the year of application than mineral fertiliser N as indicated by recovery rates of 21–22% (FNUE_15N) and 39–62% (FNUE_diff), respectively. When mineral N and slurry were applied together, the difference method estimated significantly lower N uptake efficiencies for both mineral and slurry N compared to a single application, while values obtained by the isotope method were not affected.     

Nitrogen input, <Superscript>15</Superscript>N balance and mineral N dynamics in a rice–wheat rotation in southwest China

A field experiment and farm survey were conducted to test nitrogen (N) inputs, ¹⁵N-labelled fertilizer balance and mineral N dynamics of a rice–wheat rotation in southwest China. Total N input in one rice–wheat cycle averaged about 448 kg N ha⁻¹, of which inorganic fertilizer accounted for 63% of the total. The effects of good N management strategies on N cycling were clear: an optimized N treatment with a 27% reduction in total N fertilizer input over the rotation decreased apparent N loss by 52% and increased production (sum of grain yield of rice and wheat) compared with farmers’ traditional practice. In the ¹⁵N-labelled fertilizer experiment, an optimized N treatment led to significantly lower ¹⁵N losses than farmers’ traditional practice; N loss mainly occurred in the rice growing season, which accounted for 82% and 67% of the total loss from the rotation in farmers’ fields and the optimized N treatment, respectively. After the wheat harvest, accumulated soil mineral N ranged from 42 to 115 kg ha⁻¹ in farmers’ fields, of which the extractable soil NO₃ ⁻–N accounted for 63%. However, flooding soil for rice production significantly reduced accumulated mineral N after the wheat harvest: in the ¹⁵N experiment, farmers’ practice led to considerable accumulation of mineral N after the wheat harvest (125 kg ha⁻¹), of which 69% was subsequently lost after 13 days of flooding. Results from this study indicate the importance of N management in the wheat-growing season, which affects N dynamics and N losses significantly in the following rice season. Integrated N management should be adopted for rice–wheat rotations in order to achieve a better N recovery efficiency and lower N loss.     

Characterization of fecal nitrogen forms produced by a sheep fed with <Superscript>15</Superscript>N labeled ryegrass

Little is known about nitrogen (N) forms in ruminant feces, although this information is important to understand N dynamics in agro-ecosystems. We fed ¹⁵N labeled ryegrass hay to a sheep and collected ¹⁵N labeled feces. Nitrogen forms in the feces were characterized by chemical extractions, solid-state cross polarization ¹⁵N nuclear magnetic resonance spectroscopy (SS CP/MAS ¹⁵N NMR) and Curie-point pyrolysis–gas chromatography/mass spectrometry (Cp Py-GC/MS). A 4 months incubation experiment was conducted to assess N release from the feces. Half of the fecal N could be ascribed to bacterial and endogenous debris and a third to undigested dietary N. About a tenth of the fecal N was mineralized during the incubation experiment. The ¹⁵N abundance of nitrate released during the incubation remained constant and close to the ¹⁵N abundance of the total feces N. The NMR analysis of the feces showed that most of the N was present in proteins, while some was present as heterocyclic N, amino acids and ammonium. The Cp Py-GC/MS analysis confirmed the presence of proteins, amino acids and heterocyclic N in the feces. Comparing these results to those obtained from the ¹⁵N labeled hay suggests that some N compounds present in the plant were not digested by the animal, and that the animal excreted de novo synthesized N compounds. The low content in ammonium and amino acids, the low rate of N release from these feces during the incubation and the relatively high fecal protein content, particularly the hard to mineralize undigested and microbially bound forms, can explain the low transfer of N from these feces to crops observed in a previous work.     

Plastic-film mulch and fertilization rate affect the fate of urea-<Superscript>15</Superscript>N in maize production

We investigated the effects of interaction between plastic-film mulch and nitrogen (N) fertilization rate on the fate of fertilizer N in a ridge–furrow maize (Zea mays L.) cropping system. Three N levels (0, 138 and 207 kg ha^?1, abbreviated as N0, N1 and N2) were combined with plastic-film-mulching and no-mulching, successively in 2015 and 2016, at a cold semiarid site. Within each treated plot, a micro-plot was established to trace the fate of urea-N (only ¹⁵N-labeled in 2015). Averaging 2 years, increasing fertilization from N1 to N2 increased maize grain yield and total N uptake only in mulched soils. Mulch increased both maize grain yield and total N uptake more at N2 than at N1. In 2015, mulch increased the in-season fertilizer N uptake in maize by 53% at N1 but by 75% at N2; increasing N application from N1 to N2 enhanced the fertilizer N acquisition by 26% in non-mulched but by 45% in mulched plots. In 2016, similar effects of interaction existed between mulch and fertilization rate on the residual fertilizer N uptake by maize. Mulch enhanced fertilizer N availability in the topsoil relative to no mulch, responsible for the increased maize fertilizer N uptake in mulched treatments. Decreased in-season fertilizer N loss and transformation of urea N to the organic N in mulched soils were contributors to the increased fertilizer N availability, compared to non-mulched soils. We concluded that the effects of fertilization on maize total N uptake and fertilizer N recovery benefited from plastic-film mulch.     

Field-assisted diffusion of K<Superscript>+</Superscript>, Rb<Superscript>+</Superscript>, Cs<Superscript>+</Superscript>, Ag<Superscript>+</Superscript>, and Tl<Superscript>+</Superscript> ions in sodium silicate glass

The composition of the diffusion zone formed during the interaction between 20Na₂O · 80SiO₂ glass and molten silver, rubidium, cesium, and thallium nitrates with and without imposition of a constant electric field was determined using X-ray microanalysis. The interdiffusion coefficients and values of electrical mobility were calculated, and the parameters of temperature dependence were determined. The electrical mobility was almost independent of the size and chemical nature of a cation and was determined by the mobility of the cation included into the initial glass.     

Kinetics of <Superscript>14</Superscript>C distribution after tracer dose of <Superscript>14</Superscript>C-lutein in an adult woman

Lutein is an oxygenated carotenoid (xanthophyll) found in dark green leafy vegetables. High intakes of lutein may lower the risk of age-related macular degeneration. Current understanding of human lutein metabolism as it might occur in vivo is incomplete. Therefore, we conducted a feasibility study where we dosed a normal adult woman with ¹⁴C-lutein (125 nmol, 36 nCi ¹⁴C), dissolved in olive oil (0.5 g/kg body weight) and mixed in a banana shake. Blood, urine, and feces collected before the dose was administered served to establish baseline values. There-after, blood was collected for 63 d following the dose, while feces and urine were collected for 2 wk post-dose. The ¹⁴C contents in plasma, urine, and feces were measured by accelerator MS. The ¹⁴C first appeared in plasma 1 h after dosing and reached its highest level,≈2.08% of dose/L plasma, at 14 h post-dose. The plasma pattern of ¹⁴C did not include a chylomicrons/VLDL (intestinal) peak like that when the same subject received ¹⁴C-β-carotene (a previous test), suggesting that lutein was handled differently from β-carotene by plasma lipoproteins. Lutein had an elimination half-life (t _1/2) of≈10 d. Forty-five percent of the dose of ¹⁴C was eliminated in feces and 10% in urine in the first 2 d after dosing. Quantifying human lutein metabolism is a fertile area for future research.     

Hydrothermal synthesis of zeolite L in a Na<Superscript>+</Superscript>/K<Superscript>+</Superscript> mixed alkali system

Zeolite L was prepared from the substrate system of Na₂O-K₂O-Al₂O₃-SiO₂-H₂O at temperatures of 373–443 K by hydrothermal crystallization. The influence of various synthesis parameters such as the concentration ratios of the components, starting raw materials, synthesis temperature, gel aging, and stirring on the crystallization was investigated. Investigations revealed that the crystallinity of zeolite L crystals depends on molar ratios of the components such as SiO₂/Al₂O₃, (K₂O+Na₂O)/SiO₂, Na₂O/(K₂O+Na₂O), and H₂O/(K₂O+Na₂O). Pure and highly crystalline zeolite L could be obtained from a gel with the molar composition 5.4K₂O–5.7Na₂O-Al₂O₃-30SiO₂-500H₂O after 24 h at 443 K. It was found that the silica source affected the crystal size of zeolite L, and as the synthesis temperature increased, the average crystal size became larger. The crystal size could be decreased significantly by stirring the gel or subjecting the substrate mixture to an aging treatment at room temperature prior to the hydrothermal treatment. Thermal stability of the zeolite L crystals obtained was also briefly investigated.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR characterization and stereochemical assignments of bile acids in aqueous media

The unconjugated bile acids cholic acid, deoxycholic acid, and chenodeoxycholic acid; their glycine and taurine conjugated glycocholic acid, glycodeoxycholic acid, glycochenodeoxycholic acid, taurocholic acid, taurodeoxycholic acid, and taurochenodeoxycholic acid; and a taurine conjugated ursodeoxycholic acid, tauroursodeoxycholic acid, were characterized through ¹H and ¹³C NMR in aqueous media under the physiological pH region (7.4±0.1). Assignments of ¹H and ¹³C signals of all the bile acids were made using a combination of several one- and two-dimensional, homonuclear (¹H−¹H) and heteronuclear (¹H−¹³C) correlations as well as spectral editing NMR methods. Stereochemical assignment of the five-membered ring of the bile acids is reported here for the first time. The complete characterization of various bile acids in aqueous media presented here may have implications in the study of the pathophysiology of biliary diseases through human biliary fluids using NMR spectroscopy.     

Visible up-conversion luminescence of CaWO<Subscript>4</Subscript>: Er<Superscript>3+</Superscript>,Yb<Superscript>3+</Superscript> and emission enhancement by tri-doping of Li<Superscript>+</Superscript> ions

Er³⁺,Yb³⁺ co-doped CaWO₄ polycrystalline powders were prepared by a solid-state reaction and their up-conversion (UC) luminescence properties were investigated in detail. Under 980 nm laser excitation, CaWO₄: Er³⁺,Yb³⁺ powder exhibited green UC emission peaks at 530 and 550 nm, which were due to the transitions of Er³⁺ (²H_11/2)→Er³⁺ (⁴I_15/2) and Er³⁺ (⁴S_3/2)→Er³⁺ (⁴I_15/2), respectively. Effects of Li+ tri-doping into CaWO₄: Er³⁺,Yb³⁺ were investigated. The introduction of Li⁺ ions reduced the optimum calcinations temperature about 100 °C by a liquid-phase sintering process and the UC emission intensity was remarkably enhanced by Li⁺ ions, which could be attributed to the lowering of the symmetry of the crystal field around Er³⁺ ions.     

Quantification of symbiotic nitrogen fixation by <Emphasis Type="Italic">Elaeagnus angustifolia</Emphasis> L. on salt-affected irrigated croplands using two <Superscript>15</Superscript>N isotopic methods

Afforestation with fast growing N-fixing trees is an option for ecological restoration of highly-salinized irrigated croplands, but information about the N-fixing capability of trees on saline soils is sparse. The ¹⁵N-enrichment technique (¹⁵NET) and the A value (AV) method were used to quantify in lysimeters the proportion of atmospheric N₂ (%Ndfa) fixed by Elaeagnus angustifolia L., with a reference to non-N-fixing Gleditsia triacanthos L. and Ulmus pumila L. Twenty kg N ha⁻¹ of 5 atom %¹⁵N excess ammonium nitrate (35% N) was applied to 1-year-old trees in 2007 and 2-year-olds in 2008. Since this rate was insufficient for the older reference trees, 60 kg N ha⁻¹ was applied in 2008. With ¹⁵NET, the %Ndfa of E. angustifolia in 2007 was 79% when referenced against U. pumila and 68% against G. triacanthos. With the AV method, the %Ndfa of 2-year-old E. angustifolia was 80 and 68% when referenced against U. pumila and G. triacanthos, respectively. Over 2 years, E. angustifolia fixed 17 kg N ha⁻¹ when related to U. pumila and 14 kg N ha⁻¹ with G. triacanthos (assumed density: 5,000 trees ha⁻¹). N-fixing E. angustifolia has the potential to be self-sufficient in N when planted in the strongly saline soils.     

Effects of adding B<Subscript>2</Subscript>O<Subscript>3</Subscript> as a flux on phosphorescent properties in synthesis of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: (Eu<Superscript>2+</Superscript>, DY<Superscript>3+</Superscript> phosphor

SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was prepared by solid state reaction. B₂O₅ as a flux was added in SrAl₂O₄:(Eu ²⁺, Dy³⁺) in order to accelerate a solid state reaction. In this paper, the effects of B₂O₃ on the crystal structure and the phosphorescent properties of the material have been evaluated. The synthesized phosphor exhibited a broad band emission spectrum peaking at 520 nm, and the spectrum peak showed little effect by the B₂O₃ contents. The maximum afterglow intensity of the SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was obtained at the B₂O₃ content of 5%. Adding the B₂O₃ caused uniform distortion to the crystal structure of the phosphor and resulted in reducing the lengths of a and c axes and Β angle of the SrAl₂O₄ crystal. The uniform distortion was accompanied with crystal defects which can trap the holes generated by the excitation of Eu²⁺ ions. The afterglow characteristic of the SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was thus enhanced.     

<Superscript>1</Superscript>H- and <Superscript>13</Superscript>C-NMR Characterization of the Molecular Components of the Lipid Fraction of Pecorino Sardo Cheese

In this work the molecular fatty components of Pecorino Sardo Protected Designation of Origin (PS PDO) cheese were characterized through an exhaustive investigation of the ¹H- and ¹³C-NMR spectra of the extracted lipids. Several fatty acids (FA), such as long chain saturated, oleic, linoleic, linolenic, butyric, capric, caprylic, caproic, trans vaccenic, conjugated linoleic acid (cis9, trans11–18:2), and caproleic (9–10:1) were unambiguously detected. The positional isomery of some acyl groups in the glycerol backbone of triacylglycerols (TAG) was assessed. Furthermore, the NMR signals belonging to sn-1,2/2,3, sn-1,3 diacylglycerols (DAG), and free fatty acids (FFA) were analysed as a measure of lipolytic processes on cheese. Lastly, ¹H-NMR resonances of saturated aldehydes and hydroperoxides were detected, their very low intensity indicating that the lipid oxidation process can be considered to be of minor relevance in Pecorino Sardo cheese.     

Effect of Ni<Superscript>2+</Superscript>, V<Superscript>4+</Superscript> and Mo<Superscript>6+</Superscript> concentration on iron oxidation by <Emphasis Type="Italic">Acidithiobacillus ferrooxidans</Emphasis>

The ferrous oxidation ability of Acidithiobacillus ferrooxidans was studied in the presence of Ni²⁺, V⁴⁺ and Mo⁶⁺ in 9 K media in order to implement the culture in the bioleaching of spent catalyst. The rate of iron oxidation decreased with increasing concentration of metal ions, but the rate of inhibition was metal-ion dependent. The tolerance limit was critical at a concentration of 25 g/L Ni²⁺, 5 g/L V⁴⁺ and 0.03 g/L Mo⁶⁺. The growth rate of microorganisms was negligible at concentrations of 6 g/L V⁴⁺ and 0.04 g/L Mo⁶⁺. Levels and degree of toxicity of these ions have been quantified in terms of a toxicity index (TI). The toxicity order of metal ions was found to be Mo⁶⁺>V⁴⁺>Ni²⁺. The significance and relevance of multi-metal ion tolerance in Acidithiobacillus ferrooxidans has been highlighted with respect to bioleaching of spent refinery catalyst.     

Determination of Glycerol in Wines Using <Superscript>31</Superscript>P-NMR Spectroscopy

³¹P-NMR spectroscopy was employed to detect and quantify glycerol in red wines from various regions of Greece. This novel analytical method was based on the derivatization of the hydroxyl groups of glycerol with 2-chloro-4,4,5,5-tetramethyl dioxaphospholane, and identification of the phosphitylated compound on the basis of ³¹P chemical shifts. Quantification of glycerol in wines was accomplished by integration of appropriate signals in the ³¹P-NMR spectrum and the use of the phosphitylated cyclohexanol as the internal standard. The method was reproducible (CV (%) = 2.35) and accurate (CV (%) = 1.34). Its applicability to glycerol quantification in wines was tested against a weighted amount of a glycerol-model compound by linear regression analysis (R = 0.999; intercept = 0.074 ± 0.078; slope = 0.998 ± 0.003; p = 0.000). Furthermore, the NMR method was compared to the AOAC official method (HPLC) using the Bland and Altman statistical analysis. The distribution of the data points in the bias plot showed that 100% of the measurements of glycerol in 16 wine samples from various regions of Greece were within the limits of agreement of the two methods.     

Thermal Stability and Spectral Properties of Tm<Superscript>3+</Superscript>-Yb<Superscript>3+</Superscript> CO-Doped Tellurite Glasses

Glasses of the system 75TeO₂–20ZnO–5La₂O₃–0.8Tm₂O₃–xYb₂O₃ were prepared by high temperature melt cooling method. Results of differential scanning calorimetry indicate that, all glass samples have excellent thermal stability. Judd–Ofelt strength parameters, spontaneous emission probabilities, fluorescence branching rations, fluorescence radiative lifetime of Tm³⁺ ions in tellurite glass were calculated. The impact of Yb³⁺ concentration on the fluorescence properties of Tm³⁺ ions in the S band under the pumping wavelength of 465 nm was investigated in a suggestion that, ³H₄ radiative lifetimes will be prolonged and the performance of optical amplifier gain of Tm³⁺ in tellurite glass co-doped with 0.5 mol % Yb³⁺ ions will be improved.     

Roles of doping ions in persistent luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: Eu<Superscript>2+</Superscript>,<Emphasis Type="Italic">RE</Emphasis><Superscript>3+</Superscript> phosphors

The polycrystalline Eu²⁺ and Dy³⁺ codoped strontium aluminates SrAl₂O₄: Eu²⁺,Dy³⁺ were prepared by a solid-state reaction. The UV-excited photoluminescence, persistent luminescence, and thermoluminescence of the SrAl₂O₄: Eu²⁺,Dy³⁺ phosphors with different compositions and ion doping was studied and compared. The results showed that the Eu²⁺ ion doped in SrAl₂O₄: Eu²⁺,Dy³⁺ phosphors is not only the UV-excited luminescent center but also the persistent luminescent center. The Dy³⁺ ion introduced into SrAl₂O₄: Eu²⁺ crystal matrix can hardly yield any luminescence under UV excitation but acts as an electron trap with a suitable depth for persistent luminescence. The Dy³⁺ codoping would effectively enhance the persistent luminescence and thermoluminescence. Different codoping RE ³⁺ ions have a different effect on persistent luminescence. Only the RE ³⁺ ions (for example, Dy³⁺ and Nd³⁺), which have suitable optical electronegativity, can form suitable electron traps and effectively improve the persistent luminescence of SrAl₂O₄: Eu²⁺. Based on the above observations, a persistent luminescence mechanism, electron transfer model, was proposed and illustrated. The text was submitted by the authors in English.