2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and its application for determination of amines by high performance liquid chromatography with fluorescence detection and identification with mass spectroscopy/atmospheric pressure chemical ionization

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC-HCI) as the dehydrant with fluorescence detection has been developed. Amines were derivatized to their acidamides with labeling reagent 2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA). Studies on derivatization conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum at lambda(ex) 260nm and an emission maximum at lambda(em) 380nm. The labeled derivatives exhibited high stability and were enough to be efficiently analyzed by high-performance liquid chromatography. Identification of derivatives was carried out by online post-column mass spectrometry (LC/APCI-MS/MS) and showed an intense protonated molecular ion corresponding m/z [MH](+) under APCI in positive-ion mode. At the same time, the fluorescence properties of derivatives in various solvents or at different temperature were investigated. The method, in conjunction with a gradient elution, offered a baseline resolution of the common amine derivatives on a reversed-phase Eclipse XDB-C-8 column. LC separation for the derivatized amines showed good reproducibility with acetonitrile-water as mobile phase. Detection limits calculated from 0.78 pmol injection, at a signal-to-noise ratio of 3, were 3.1-18.2 fmol. The mean intra- and inter-assay precision for all amine levels were < 3.85% and 2.11%, respectively. Excellent linear responses were observed with coefficients of > 0.9996. The established method for the determination of aliphatic amines from real wastewater and biological samples was satisfactory. (c) 2006 Elsevier B.V. All rights reserved.

Particle Image Velocimetry Investigation of a finite amplitude pressure wave

Particle image velocimetry is used to study the motion of gas within a duct subject to the passage of a finite amplitude pressure wave. The wave is representative of the pressure waves found in the exhaust systems of internal combustion engines. Gas particles are accelerated from stationary to 150 m/s and then back to stationary in 8 ms. It is demonstrated that gas particles at the head of the wave travel at the same velocity across the duct cross section at a given point in time. Towards the tail of the wave viscous effects are plainly evident causing the flow profile to tend towards parabolic. However, the instantaneous mean particle velocity across the section is shown to match well with the velocity calculated from a corresponding measured pressure history using 1D gas dynamic theory. The measured pressure history at a point in the duct was acquired using a high speed pressure transducer of the type typically used for engine research in intake and exhaust systems. It is demonstrated that these are unable to follow the rapid changes in pressure accurately and that they are prone to resonate under certain circumstances.

Acoustic, volumetric, compressibility and refractivity properties and Flory’s reduction parameters of some homologous series of alkyl alkanoates from 298.15 to 333.15 K

The speeds of sound u in, densities ? and refractive indices nD of some homologous series, such as n-alkyl ethanoates, n-alkyl propionates, methyl alkanoates, ethyl alkanoates, dialkyl malonates, and alkyl haloalkanoates, were measured in the temperature range from 298.15 to 333.15 K. Molar volume V, isentropic and isothermal compressibilities ?S and ?T, molar refraction Rm, Eykman’s constant Cm, molecular radius r, Rao’s molar function R, thermal expansion coefficient a, thermal pressure coefficient ?, and Flory’s characteristic parameters image, P*, V*, and T* have been calculated from the measured experimental data. Applicability of Rao theory and Flory–Patterson–Pandey (FPP) theory have been examined and discussed for these alkanoates.

Acoustic, volumetric, compressibility and refractivity properties and reduction parameters for the ERAS and Flory models of some homologous series of amines from 298.15 to 328.15 K

The speeds of sound u, densities ? and refractive indices nD of homologous series of mono-, di-, and tri-alkylamines were measured in the temperature range from 298.15 to 328.15 K. Isentropic and isothermal compressibilities ?S and ?T, molar refraction Rm, Eykman’s constant Cm, Rao’s molar sound function R, thermal expansion coefficient a, thermal pressure coefficient ?, and reduction parameters P*, V*, and T* in frameworks of the ERAS model for associated amines and Flory model for tertiary amines have been calculated from the measured experimental data. Applicability of the Rao theory and the ERAS and Flory models have been examined and discussed for the alkyl amines.

PVT Property Measurements for Some Aliphatic Esters from (298 to 393) K and up to 35 MPa

The results of PVT measurements of the liquid phase within the temperature range of (298 to 393) K and up to 35 MPa are presented for some aliphatic esters. Measurements were made by means of a vibrating-tube densimeter, model DMA 512P from Anton Parr. The calibration of the densimeter was performed with water and n-heptane as reference fluids. The experimental PVT data have been correlated by a Tait equation. This equation gives excellent results when used to predict the density of the esters using the method proposed by Thomson et al. (AIChE J. 1982, 28, 671-676). Isothermal compressibilities, isobaric expansivities, thermal pressure coefficients, and changes in the isobaric heat capacity have been calculated from the volumetric data.

Developing a reliable strategy to infer the effective soil hydraulic properties from field evaporation experiments for agro-hydrological models

The Richards equation has been widely used for simulating soil water movement. However, the take-up of agro-hydrological models using the basic theory of soil water flow for optimizing irrigation, fertilizer and pesticide practices is still low. This is partly due to the difficulties in obtaining accurate values for soil hydraulic properties at a field scale. Here, we use an inverse technique to deduce the effective soil hydraulic properties, based on measuring the changes in the distribution of soil water with depth in a fallow field over a long period, subject to natural rainfall and evaporation using a robust micro Genetic Algorithm. A new optimized function was constructed from the soil water contents at different depths, and the soil water at field capacity. The deduced soil water retention curve was approximately parallel but higher than that derived from published pedo-tranfer functions for a given soil pressure head. The water contents calculated from the deduced soil hydraulic properties were in good agreement with the measured values. The reliability of the deduced soil hydraulic properties was tested in reproducing data measured from an independent experiment on the same soil cropped with leek. The calculation of root water uptake took account for both soil water potential and root density distribution. Results show that the predictions of soil water contents at various depths agree fairly well with the measurements, indicating that the inverse analysis is an effective and reliable approach to estimate soil hydraulic properties, and thus permits the simulation of soil water dynamics in both cropped and fallow soils in the field accurately. (C) 2009 Elsevier B.V. All rights reserved.

The XWS open access catalogue of extreme European windstorms from 1979 to 2012

The XWS (eXtreme WindStorms) catalogue consists of storm tracks and model-generated maximum 3 s wind-gust footprints for 50 of the most extreme winter windstorms to hit Europe in the period 1979–2012. The catalogue is intended to be a valuable resource for both academia and industries such as (re)insurance, for example allowing users to characterise extreme European storms, and validate climate and catastrophe models. Several storm severity indices were investigated to find which could best represent a list of known high-loss (severe) storms. The best-performing index was Sft, which is a combination of storm area calculated from the storm footprint and maximum 925 hPa wind speed from the storm track. All the listed severe storms are included in the catalogue, and the remaining ones were selected using Sft. A comparison of the model footprint to station observations revealed that storms were generally well represented, although for some storms the highest gusts were underestimated. Possible reasons for this underestimation include the model failing to simulate strong enough pressure gradients and not representing convective gusts. A new recalibration method was developed to estimate the true distribution of gusts at each grid point and correct for this underestimation. The recalibration model allows for storm-to-storm variation which is essential given that different storms have different degrees of model bias. The catalogue is available at www.europeanwindstorms.org.

Surface modification of siloxane containing polyurethane polymer by dielectric barrier discharge at atmospheric pressure

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Treatment of polycarbonate by dielectric barrier discharge (DBD) at atmospheric pressure

Generally most plastic materials are intrinsically hydrophobic, low surface energy materials, and thus do not adhere well to other substances. Surface treatment of polymers by discharge plasmas is of great and increasing industrial application because it can uniformly modify the surface of sample without changing the material bulk properties and is environmentally friendly. The plasma processes that can be conducted under ambient pressure and temperature conditions have attracted special attention because of their easy implementation in industrial processing. Present work deals with surface modification of polycarbonate (PC) by a dielectric barrier discharge (DBD) at atmospheric pressure. The treatment was performed in a parallel plate reactor driven by a 60Hz power supply. The DBD plasmas at atmospheric pressure were generated in air and nitrogen. Material characterization was carried out by contact angle measurements, and X-ray photoelectron spectroscopy (XPS). The surface energy of the polymer surface was calculated from contact angle data by Owens-Wendt method using distilled water and diiodomethane as test liquids. The plasma-induced chemical modifications are associated with incorporation of polar oxygen and nitrogen containing groups on the polymer surface. Due to these surface modifications the DBD-treated polymers become more hydrophilic. Aging behavior of the treated samples revealed that the polymer surfaces were prone to hydrophobic recovery although they did not completely recover their original wetting properties.

Dynamic properties of wood using the Split-Hopkinson Pressure Bar

Strain rate significantly affects the strength of a material. The Split-Hopkinson Pressure Bar (SHPB) was initially used to study the effects of high strain rate (~103 1/s) testing of metals. Later modifications to the original technique allowed for the study of brittle materials such as ceramics, concrete, and rock. While material properties of wood for static and creep strain rates are readily available, data on the dynamic properties of wood are sparse. Previous work using the SHPB technique with wood has been limited in scope to variability of only a few conditions and tests of the applicability of the SHPB theory on wood have not been performed. Tests were conducted using a large diameter (3.0 inch (75 mm)) SHPB. The strain rate and total strain applied to a specimen are dependent on the striker bar length and velocity at impact. Pulse shapers are used to further modify the strain rate and change the shape of the strain pulse. A series of tests were used to determine test conditions necessary to produce a strain rate, total strain, and pulse shape appropriate for testing wood specimens. Hard maple, consisting of sugar maple (Acer saccharum) and black maple (Acer nigrum), and eastern white pine (Pinus strobus) specimens were used to represent a dense hardwood and a low-density soft wood. Specimens were machined to diameters of 2.5 and 3.0 inches and an assortment of lengths were tested to determine the appropriate specimen dimensions. Longitudinal specimens of 1.5 inch length and radial and tangential specimens of 0.5 inch length were found to be most applicable to SHPB testing. Stress/strain curves were generated from the SHPB data and validated with 6061-T6 aluminum and wood specimens. Stress was indirectly corroborated with gaged aluminum specimens. Specimen strain was assessed with strain gages, digital image analysis, and measurement of residual strain to confirm the strain calculated from SHPB data. The SHPB was found to be a useful tool in accurately assessing the material properties of wood under high strain rates (70 to 340 1/s) and short load durations (70 to 150 μs to compressive failure).

Age models, color measurements, and calculated sea surface temperatures of sediment cores from the Bering Sea and the Sea of Okhotsk

Past changes in North Pacific sea surface temperatures and sea-ice conditions are proposed to play a crucial role in deglacial climate development and ocean circulation but are less well known than from the North Atlantic. Here, we present new alkenone-based sea surface temperature records from the subarctic northwest Pacific and its marginal seas (Bering Sea and Sea of Okhotsk) for the time interval of the last 15 kyr, indicating millennial-scale sea surface temperature fluctuations similar to short-term deglacial climate oscillations known from Greenland ice-core records. Past changes in sea-ice distribution are derived from relative percentage of specific diatom groups and qualitative assessment of the IP25 biomarker related to sea-ice diatoms. The deglacial variability in sea-ice extent matches the sea surface temperature fluctuations. These fluctuations suggest a linkage to deglacial variations in Atlantic meridional overturning circulation and a close atmospheric coupling between the North Pacific and North Atlantic. During the Holocene the subarctic North Pacific is marked by complex sea surface temperature trends, which do not support the hypothesis of a Holocene seesaw in temperature development between the North Atlantic and the North Pacific.

Petrophysical investigation on sediment core CRP-3 from the Ross Sea, Antarctica

A suite of petrophysical properties - velocity, resistivity, bulk density, porosity, and matrix density - was measured on 88 core plugs from the CRP-3 drillhole. Core-plug bulk densities were used to recalibrate both whole-core and downhole bulk density logs. Core-plug measurements of matrix density permit conversion of the whole-core and downhole bulk density logs to porosity. Both velocity and formation factor (a normalized measure of resistivity) are strongly correlated with porosity. The velocity/porosity pattern is similar to that for the lower part of CRP-2A and is consistent with the empirical relationship for sandstones. Core-plug and whole-core measurements of P-wave velocity at atmospheric pressure exhibit excellent agreement. Measurements of velocity as a function of pressure indicate a significantly higher velocity sensitivity to pressure than has been observed at CRP-1 and CRP-2A; rebound or presence of microcracks at CRP-3 may be responsible. The percentage difference between velocities at in situ pressures and atmospheric pressures increases downhole from 0% at the seafloor to 9% at the bottom. This pattern can be used to correct whole-core velocity data, measured at atmospheric pressure, to in situ velocities for depth-to-time conversion and associated comparison to the seismic profile across the drillsite

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Hydrographic measurements from C.S.S. Hudson Cruise 82-002, Canadian Technical Report of Hydrography and Ocean Sciences No. 118, 112 pp (digital version)

This archive consists of the hydrographic data collected on Cruise 82-002 of C.S.S. Hudson, April 11 to May 2, 1982. 78 stations were occupied on a line running near 48°N from the mouth of the English Channel to the Grand Banks of Newfoundland. Pressure, temperature and salinity were measured by a Guildline digital CTP system. Salinity, dissolved oxygen, silicate, nitrate and phosphate were measured from water samples collected on the CTP upcasts. CTP and discrete bottle data and associated derived parameters are tabulated at standard levels. This is the digital version of the printed report (of 1989, see further details), published in 2006 with the information system Pangaea.