Multielement (H,C, N,O, S) stable isotope characteristics of lamb meat from different Italian regions

The study focuses on the ²H/H, ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O and ³⁴S/³²S values of defatted dry matter (DFDM) and on the ²H/H, ¹³C/¹²C and ¹⁸O/¹⁶O values of the fat fraction of meat samples from various lamb types reared in seven Italian regions, following different feeding regimes (forage, concentrate, milk). The ¹³C/¹²C (r = 0.922), ²H/H (r = 0.577) and ¹⁸O/¹⁶O (r = 0.449) values of fat and DFDM are significantly correlated, the fat values being significantly lower for C and H and higher for O than for DFDM values and the differences between the two fractions not being constant for different lamb types. The feeding regime significantly affected the ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O and ²H/H of fat. The DFDM ²H/H, and ¹⁸O/¹⁶O values, excluding an outlier, are significantly correlated with the corresponding values in meteoric waters, thus allowing us to trace the variability of geoclimatic factors. ¹⁵N/¹⁴N is influenced by pedoclimatic conditions, whereas ³⁴S/³²S is influenced by the sea spray effect and the surface geology of the provenance area. By applying stepwise linear discriminant analysis only the ²H/H of fat was found not to be significant and 97.7% of the samples were correctly assigned to the lamb type and more than 90% cross‐validated. With the feeding regime, 97.7% of the samples were both correctly assigned and cross‐validated using a predictive model including ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O, ³⁴S/³²S of DFDM and ¹⁸O/¹⁶O of fat. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies of the vertical distribution of134Cs,137Cs,238Pu,239, 240Pu,241Pu,241Am and210Pb in ombrogenous mires at mid-latitudes

Six peat cores taken from three unmodified blanket and raised bogs in Ireland were sectioned and analyzed for a range of radionuclides including¹³⁴Cs,¹³⁷Cs,²³⁸Pu,²³⁹Pu,²⁴¹Am, and²¹⁰Pb.¹³⁴Cs and¹³⁷Cs were measured by high resolution gamma-spectrometry, while the transuranium nuclides were determined after chemical separation by alpha-spectrometry.²⁴¹Pu, present on the electroplated discs together with Pu(), was measured directly by low-level liquid scintillation counting. Core chronologies were established by measuring the unsupported²¹⁰Pb component using low energy photon spectrometry (LEPS). From the resulting profiles, relaxation depths and migration rates for the above mentioned radionuclides have been determined and differences in the values of these parameters interpreted.²³⁸Pu/^239,240Pu and²⁴¹Pu/^239,240Pu ratios have been examined carefully and are discussed in some detail. Finally, the contribution from Chernobyl to the total radiocaesium inventory in each core has been established using the¹³⁴Cs/¹³⁷Cs ratio observed in the initial fallout from Chernobyl.     

Separation of 3H, 14C, 32P, 35S, 125I, and 131I in radioisotope waste

Measurement of ³H, ¹⁴C, ³²P, ³⁵S, ¹²⁵I, and ¹³¹I in radioisotope (RI) waste materials such as the vials, pipette tips, tubes, syringes, and paper generated from the industrial, medical, educational, and research organizations were conducted by a wet oxidation method. Counts were obtained by a liquid scintillation counter for ³H, ¹⁴C, and ³²P; a gas proportional counter for ³⁵S; a low energy photon spectroscopy for ¹²⁵I; and an HPGe detector for ¹³¹I. After the treatment of approximately 20 g of the sample, the counting value was determined to obtain a minimum detectable activity (MDA) of approximately 1 × 10^?3 ~ 5 × 10^?2 Bq/g. The specific activities of shor-half-life RIs (³²P, ³⁵S, ¹²⁵I, and ¹³¹I) were not detectable and/or resulted in a low value (<1 Bq/g). The waste containing ³H and ¹⁴C was observed to have the specific activities in the range of 10^?2–10⁵ and 10^?2–10⁴ Bq/g, respectively.     

Estimation of growth rate of hokutolite from Tamagawa hot-spring,Akita, Japan

The concentrations of radium isotopes and the progenies (²²⁶Ra; ²²⁸Ra and ²²⁸Th) in three hokutolite samples from Tamagawa hot-spring were measured. These isotopes were analyzed by a well-type HPGe γ-ray spectrometer for the 351, 911 and 583 keV γ-ray from ²¹⁴Pb, ²²⁸Ac and ²⁰⁸Tl, respectively, each being in radioactive equilibrium with precursors. Concentration of ²²⁶Ra and ²²⁸Ra were observed to be in the range of 52–85 and 7.1–85 Bq/g, respectively. The activity ratios of ²²⁸Ra/²²⁶Ra and ²²⁸Th/²²⁶Ra provided the estimation of the growth rate (0.09–0.15 mm/y). Estimated ²²⁸Ra/²²⁶Ra activity ratios in hot-spring water from surface of three hokutolite were concordant.     

Thermodynamic Properties of Tetraphenyltetrahydroxycyclotetrasiloxane,Octaphenyltetrahydroxytricyclooctasiloxane, Octaphenylpentacyclosilsesquioxane,and Polyphenylsilsesquioxane in the Range 0-300 K

The temperature dependences of the heat capacities of crystalline tetraphenyltetrahydroxycyclotetrasiloxane, octaphenyltetrahydroxytricyclooctasiloxane, and octaphenylpentacyclosilsesquioxane and of glassy polyphenylsilsesquioxane were measured in the range 6-300 K with an adiabatic vacuum calorimeter, with an accuracy of 0.3%. From these data, the thermodynamic functions C ⁰ _p (T), H ⁰(T) - H ⁰(0), S ⁰(T) - S ⁰(0), and G ⁰(T) - H ⁰(0) of these substances were calculated for the range 0-300 K. The standard entropies of their formation from elements at 298.15 K, _f S ⁰, and the entropies of mutual transformations of these substances in the range 0-298.15 K were calculated.     

Extraction behaviors of Eu,Th, U and Am with diamides+thenoyltrifluoroacetone

N,N-dimethyl-N,N-dihexyl-3-oxapentanediamide, DMDHOPDA, N,N-dihexyl-3-thiopentanediamide, DHTPDA and N,N-dihexyl-3-oxapentanediamide, DHOPDA were synthesized and tested for the synergistic extraction of Eu³⁺, Th⁴⁺, UO ₂ ²⁺ , NpO ₂ ⁺ and Am³⁺ with thenoyltrifluoroacetone (HTTA). Although Eu³⁺, Th⁴⁺, UO ₂ ²⁺ and Am³⁺ were not extracted by DHTPDA or DHOPDA alone, they were extracted synergistically when combined with HTTA. Analysis of the dependency of extraction on pH and extractant concentration indicated that the dominant extracted species were Eu(TTA)₃(A), Th(TTA)₃(A)(X), UO₂(TTA)₂(A) and Am(TTA)₃(A) (where A is diamide, and X is chloroacetate or ClO ₄ ^– ).     

Vertical Profiles, Inventories, and Activity Ratios of 239+240Pu and 137Cs in Sediments from Sagami Bay, Western Northwest Pacific Margin

Marine sediment cores were taken from Sagami Bay of the western Northwest Pacific and analyzed for ^239+240Pu and ¹³⁷Cs activities. A significant correlation was observed between ^239+240Pu and ¹³⁷Cs activities in sediment cores, i.e., their vertical profiles. The measured activities which were used to obtain the inventories of ^239+240Pu and ¹³⁷Cs in the sediment column, showed large variations, ranging from 36 to 474 MBq/km² for ^239+240Pu and 49 to 652 MBq/km² for ¹³⁷Cs. ^239+240Pu inventories in the sediment from one region in the Bay, Sagami Nada were 5–10 times greater than those predicted from atmospheric global fallout 42 MBq/km² at the same latitude. On the other hand, ¹³⁷Cs inventories, with a mean value of 297±168 MBq/km², were much less than predicted, 2040 MBq/km². The activity ratios of ^239+240Pu/¹³⁷Cs obtained, with a mean of 0.65±0.17, were significantly greater than the ratio predicted from fallout, 0.021. Furthermore, there was a clear relationship between both ^239+240Pu and ¹³⁷Cs inventories and the water content, indicating that higher inventories may be attributed principally to concentration in, and scavenging by, fine-grained particles.     

Synthesis of New Benzylic Di-, Tri-, and Tetraphosphonic Acids as Potential Chelating Agents

Abstract

New di-, tri-, and tetraphosphonic acids were synthesized starting from four o-hydroxymethyl phenol derivatives and obtained in three steps in good overall yield. The phosphonic acids were isolated and purified using semi-preparative C₁₈ HPLC column. The new compounds were characterized using different spectroscopic methods (¹H, ¹³C, and ³¹P NMR; ESI MS; and MSⁿ, IR).

GRAPHICAL ABSTRACT     

Characterisation of thin sputtered silicon nitride films by NRA, ERDA, RBS and SEM

Summary Thin, amorphous silicon nitride (a-SIN_x) films were deposited on n-type (100) silicon substrates using an argon ion beam for sputtering a HPSN block under high vacuum conditions. The substrates were kept at room temperature. Nitrogen depth distributions were determined by NRA using the resonance reaction ¹⁵N(p,)¹²C at 429 keV. Hydrogen profiles were analysed by NRA (¹H(¹⁵N,)¹²C at E_o=6.385 MeV) and by ERDA (²⁰Ne²⁺, E_o=10 MeV). The NRA was used to determine the depth distributions (concentration vs. areal density) of nitrogen and hydrogen taking calibration standards into consideration. The silicon depth distributions and the N/Si ratios of the deposited a-SiN_x films were determined by RBS (⁴He⁺, E_o=2.0 MeV). Film thicknesses were obtained by SEM. The density of the deposited a-SiN_x films was found to be =2.7 (±0.1) g/cm³ by correlating RBS data and real film thicknesses as obtained by SEM.     

The reaction energies of ethylene, CO, and N2 with proton, hydrogen atom, and hydride ion

It is shown by quantum chemical simulation (MP2/aug-cc-pVTZ) that the energy of addition of H⁺, H^·, and H^? decreases in the order ethylene, CO, and N₂. The energies of additions of CF₄, dimethyl ether, and BF₃ to the ions and radicals formed were calculated. Unlike the CH₃CH₂ ^? ion, the HCO^? ion can add exothermically not one, but two BF₃ molecules.     

Distribution and behaviour of99Tc,237Np,239,240Pu,and241Am in the coastal and estuarine sediments of the Irish Sea

Intertidal coastal and estuarine sediments from 24 sites in the Irish Sea have been analyzed for⁹⁹Tc,²³⁷Np,²³⁸Pu,^239,240Pu and²⁴¹Am. The²³⁷Np activity and²³⁹Pu/²⁴⁰Pu ratio were measured simultaneously by ICP-MS, and⁹⁹Tc was determined by HR-ICP-MS which is ten times more sensitive than Q-ICP-MS.The activities of⁹⁹Tc,²³⁷Np,^239,240Pu and²⁴¹Am were distributed over a wide range of 1.5–70.5, 0.01–13.3, 2.3–1589, 2.6–1894 Bq/kg, respectively. Activities of these radionuclides decreased exponentially with distance from the Sellafield source. The²⁴¹Am/^239,240Pu and²³⁷Np/^239,240Pu ratios were almost constant with distance from the Sellafield. This result suggests that the distribution and behavior of Np and Pu are controlled by complicated factors such as the influence of transport, the variation with time of Np/Pu ratio in the Sellafield discharges and sedimentary mixing processes in the Irish Sea.     

238Pu, 239+240Pu, 241Am, 90Sr and 137Cs in mountain soil samples from the Tatra National Park (Poland)

Activity concentrations and inventory for ²³⁸Pu, ^239+240Pu, ²⁴¹Am, ⁹⁰Sr, and ¹³⁷Cs in soil from Tatra Mountains of Poland are presented. Soil samples were collected using 10 cm diameter cores down to 10 cm and sliced into 3 slices. Details of the applied procedure are described with the quality assurance program. The maximum activity concentrations found for various samples were: 1782±13 Bq/kg, 17.4±0.9 Bq/kg, 3.4±0.3 Bq/kg and 84±7 Bq/kg for ¹³⁷Cs, ^239+240Pu, ²⁴¹Am and ⁹⁰Sr, respectively. The maximum cumulated deposition of ^239+240Pu is 201±8 Bq/m². The origin of radionuclides is discussed, based mostly on the observed isotopic ratio of Pu. Significant correlations were found between ^239+240Pu, ²⁴¹Am and ¹³⁷Cs. The effective vertical migration rate seems to be in the order of: ⁹⁰Sr≫Pu>Am>Cs.     

Simultaneous determination of238Pu,239+240Pu,241Pu,241Am,242Cm,244Cm,89Sr,and90Sr in vegetation samples,and application to Chernobyl-fallout contaminated grass

A radiochemical procedure is described for the simultaneous determination of²³⁸Pu,^239+240Pu,²⁴¹Pu,²⁴¹Am,²⁴²Cm,²⁴⁴Cm,⁸⁹Sr, and⁹⁰Sr in vegetation samples. The method was applied for the determination of these, radionuclides in grass, collected near Munich after the fallout from the reactor accident at Chernobyl, USSR. The specific activities observed were (in Bq kg^–1 dry weight):²³⁸Pu, 0.077;^239+240Pu, 0.15;²⁴¹Pu, 3.9;²⁴¹Am, 0.031;²⁴²Cm, 3.0;²⁴⁴Cm, 0.008;⁸⁹Sr, 2000;⁹⁰Sr, 99.     

Di-tert-butyl(N-pyrrolyl)phosphane,-sulfide, and-selenide, studied by multinuclear magnetic resonance

 Di-tert-butyl(N-pyrrolyl)phosphane (1),-sulfide (2) and-selenide (3) were studied by ¹H, ¹³C, ¹⁵N, ³¹P and ⁷⁷Se NMR spectroscopy in solution. Restricted rotation about the P–N bond was observed for 1 (ΔG^≠ _C≈58.5 kJ/mol) and 2, 3 (ΔG^≠ _C≈45 kJ/mol) by ¹H and ¹³C NMR at variable temperature. The fairly high pyrrolyl rotation barrier in 1 is ascribed to the expected steric effects exerted by the tert-butyl groups and to repulsion between the lone pairs of electrons at the phosphorus and nitrogen atoms. These repulsive forces are reduced in 2 or 3, or in di-tert-butyl(phenyl) phosphane (ΔG^≠ _C≈44 kJ/mol). Signs of coupling constants ⁿJ(³¹P, ¹³C) and ⁿ⁺¹J(³¹P, ¹H) (n=2, 3) were determined by two-dimensional (2D) ¹³C/¹H heteronuclear shift correlations. The preferred orientation of the pyrrolyl group in 1 is evident from the coupling constants ²J(³¹P, ¹³C(2))=+35.4 Hz and ²J(³¹P, ¹³C(5))=−9.3 Hz, typical of C(2) in syn and C(5) in anti position with respect to the assumed axis of the phosphorus lone pair. Hahn-echo extended (HEED) polarization transfer pulse sequences served for measuring ¹J(³¹P, ¹⁵N) and isotope induced chemical shifts ¹Δ^15/14N(³¹P) from ³¹P NMR spectra. Received: 4 April 1996/Revised: 6 May 1996/Accepted: 11 May 1996     

Yields and average cross sections of recoil charged particle induced reactions on11B,12C,13C,14N,16O and18O

The yield and average cross section for the reactions¹¹B(p, n)¹¹C,¹²C(p, )¹³N,¹³C(p, n)¹³N, ₁₂ ¹² C(d, n)¹³N,¹⁴N(p, )¹¹C,¹⁶O(p, )¹³N,¹⁶O(d, n)¹⁷F,¹⁶O(t, n)¹⁸F, and¹⁸O(p, n)¹⁸F have been measured in different compounds. The charged particles were created in the samples themselves either through recoil by scattering of 14 MeV neutrons off hydrogen and deuterium, or by the (n, t) reaction on⁶Li using thermal neutrons. The yields of reactions¹²C(d, n);¹⁶O(p, );¹⁶O(t, n) and¹⁸O(p, n) have been measured using proton, deuteron and triton spectra generated by 14 MeV neutrons in the reactions D(n, p)2n;⁶Li(n, d);⁷Li(n, d) and¹⁰B(n, d);⁷Li(n, t) and¹⁰B(n, t), respectively.     

Maple syrup analysis for137Cs,K, and B,using a low-background counting system and PGAA

Fifteen maple syrups were analyzed for¹³⁷Cs and K (via⁴⁰K) by using a low-background -ray counting system, and for B and K by using neutron capture prompt -ray activation analysis (PGAA). For low-background -ray counting, 3 limits of detection (24-hour counts) were 0.03 Bq¹³⁷Cs/kg and 10 mg K/kg for 3.5-L portions and 0.08 Bq¹³⁷Cs/kg and 20 mg K/kg for 1.0-L portions. K concentrations determined by the two methods (using 2-g portions for PGAA) were in excellent agreement. The products were obtained in 1991, with one produced in Maryland, three in New York, four in Pennsylvania, two in New Hampshire, and five in Canada. The average activity concentration for Canadian syrups (2.8 Bq¹³⁷Cs/kg) was nearly a factor of 20 greater than the average (0.15 Bq¹³⁷Cs/kg) for the other syrups, but all¹³⁷Cs activity concentrations were at least 100 times lower than those for which controls would be recommended according to Federal Radiation Council guidance. The data exhibited distinct groupings related to the sources of the products when the ratios of¹³⁷Cs activity to K content (Bq_Cs/mg_K) were plotted vs. B concentrations.     

Purification, characterization, kinetic properties, and thermal behavior of extracellular polygalacturonase produced by filamentous fungus Tetracoccosporium sp

For the first time, a polygalacturonase from the culture broth of Tetracoccosporium sp. was isolated and incubated at 30°C in an orbital shaker at 160 rpm for 48h. The enzyme was purified by ammonium sulfate precipitation and two-step ion-exchange chromatography and had an apparent molecular mass of 36 kDa, as shown by sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis. Its optimum activity was at pH 4.3 and 40°C, and the K _m and V _max values of this enzyme (for polygalacturonic acid) were 3.23 mg/mL and 0.15 μmol/min, respectively. Ag⁺, Co²⁺, EDTA, Tween-20, Tween-80, and Triton X-100 stimulated polygalacturonase activity whereas Al³⁺, Ba²⁺, Ca²⁺, Fe²⁺, Fe³⁺, Ni²⁺, Mg²⁺, Mn²⁺, and SDS inhibited it. In addition, iodoacetamide and iodoacetic acid did not inhibit enzyme activity at a concentration of 1 mM, indicating that cysteine residues are not part of the catalytic site of polygalacturonase. We studied the kinetic properties and thermal inactivation of polygalacturonase. This enzyme exhibited a t _1/2 of 63 min at 60°C and its specific activity, turnover number, and catalytic efficiency were 6.17 U/mg, 113.64 min⁻¹, and 35.18 mL/(min·mg), respectively. The activation energy (ΔE ^#) for heat inactivation was 5.341 kJ/mol, and the thermodynamic activation parameters ΔG ^#, ΔH ^#, and ΔS ^# were also calculated, revealing a potential application for the industry.     

Determination of131I,134Cs,137Cs in plants and cheese after Chernobyl accident in Roumania

Various samples from the south-east region of Roumania/greens, fodder, cheese/were analyzed for¹³¹I,¹³⁴Cs and¹³⁷Cs concentrations in May and July 1986 by -ray spectrometry. The concentrations are reported in nCi. kg^–1 wet weight. For greens, a considerable decrease was observed for¹³¹I/to 3.0–7.0 nCi. kg^–1/,¹³⁴Cs/to 0.5–2.0 nCi.kg^–1/ and¹³⁷Cs /to 1.0–4.0 nCi. kg^–1/ from the first half /5–15 May/ till the end of May 1986. For cheese, maximum values were measured between 5 and 15 May /sheep cottage cheese: 500–800 nCi.kg^–1 for¹³¹I, 25–50 nCi. kg^–1 for¹³⁴Cs, 40–80 nCi. kg^–1 for¹³⁷Cs/; at the beginning of July a considerable decrease /to 5–10 nCi. kg^–1 for¹³¹I, 1.2–2.0 nCi.kg^–1 for¹³⁴Cs, 2.2–3.0 nCi. kg^–1 for¹³⁷Cs/ was observed. In autumn 1986 a small increase up to 2.0–3.0 nCi. kg^–1 for¹³⁴Cs and 3.4–5.0 nCi. kg^–1 for¹³⁷Cs /in November/ was reported. The population's internal possible contamination was strongly limited by the authorities' severe control of the food-stuff.     

Di-tert-butyl(N-pyrrolyl)phosphane,-sulfide, and-selenide, studied by multinuclear magnetic resonance

 Di-tert-butyl(N-pyrrolyl)phosphane (1),-sulfide (2) and-selenide (3) were studied by ¹H, ¹³C, ¹⁵N, ³¹P and ⁷⁷Se NMR spectroscopy in solution. Restricted rotation about the P–N bond was observed for 1 (ΔG^≠ _C≈58.5 kJ/mol) and 2, 3 (ΔG^≠ _C≈45 kJ/mol) by ¹H and ¹³C NMR at variable temperature. The fairly high pyrrolyl rotation barrier in 1 is ascribed to the expected steric effects exerted by the tert-butyl groups and to repulsion between the lone pairs of electrons at the phosphorus and nitrogen atoms. These repulsive forces are reduced in 2 or 3, or in di-tert-butyl(phenyl) phosphane (ΔG^≠ _C≈44 kJ/mol). Signs of coupling constants ⁿJ(³¹P, ¹³C) and ⁿ⁺¹J(³¹P, ¹H) (n=2, 3) were determined by two-dimensional (2D) ¹³C/¹H heteronuclear shift correlations. The preferred orientation of the pyrrolyl group in 1 is evident from the coupling constants ²J(³¹P, ¹³C(2))=+35.4 Hz and ²J(³¹P, ¹³C(5))=−9.3 Hz, typical of C(2) in syn and C(5) in anti position with respect to the assumed axis of the phosphorus lone pair. Hahn-echo extended (HEED) polarization transfer pulse sequences served for measuring ¹J(³¹P, ¹⁵N) and isotope induced chemical shifts ¹Δ^15/14N(³¹P) from ³¹P NMR spectra. Received: 4 April 1996/Revised: 6 May 1996/Accepted: 11 May 1996     

Excitation characteristics of elements above Z=30 with57Co,67Ga,75Se,99mTc,111In,125I and201Tl implant sources

Radioactive implant induced X-ray emission (RIXE) spectrometry was examined by mixing a sample in solution with a radioisotope. The radioisotopes of⁵⁷Co,⁶⁷Ga,⁷⁵Se,^99mTc,¹¹¹In,¹²⁵I and²⁰¹Tl were used as implant X-ray excitation sources. Copper, strontium, iodine, barium, lead and uranium solutions were used as samples to be analyzed. K X-ray for all samples and L X-rays for lead and uranium samples were measured with a pure Ge detector. The excitation characteristics of each radioisotope are discussed using the effective excitation efficiency (eff) defined by the equation eff=N_c/(N_aN_d), where N_c is the number of counts in the X-ray peaks, N_a is the number of atoms of interest in the sample, and N_d is the total number of decays of radioisotope for the counting interval.