Radiative efficiencies and global warming potentials using theoretically determined absorption cross-sections for several hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs)

Integrated infrared cross-sections and wavenumber positions for the vibrational modes of a range of hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs) have been calculated. Spectra were determined using a density functional method with an empirically derived correction for the wavenumbers of band positions. Radiative efficiencies (REs) were determined using the Pinnock et al. method and were used with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). For the HFEs and the majority of the molecules in the HG series HFPEs, theoretically determined absorption cross-sections and REs lie within ca. 10% of those determined using measured spectra. For the larger molecules in the HG series and the HG′ series of HFPEs, agreement is less good, with theoretical values for the integrated cross-sections being up to 35% higher than the experimental values; REs are up to 45% higher. Our method gives better results than previous theoretical approaches, because of the level of theory chosen and, for REs, because an empirical wavenumber correction derived for perfluorocarbons is effective in predicting the positions of C–F stretching frequencies at around 1250 cm−1 for the molecules considered here.

Water vapour continuum absorption in near-infrared windows derived from laboratory measurements

In most near-infrared atmospheric windows, absorption of solar radiation is dominated by the water vapor self-continuum and yet there is a paucity of measurements in these windows. We report new laboratory measurements of the self-continuum absorption at temperatures between 293 and 472 K and pressures from 0.015 to 5 atm in four near-infrared windows between 1 and 4 m (10000-2500 cm-1); the measurements are made over a wider range of wavenumber, temperatures and pressures than any previous measurements. They show that the self-continuum in these windows is typically one order of magnitude stronger than given in representations of the continuum widely used in climate and weather prediction models. These results are also not consistent with current theories attributing the self continuum within windows to the far-wings of strong spectral lines in the nearby water vapor absorption bands; we suggest that they are more consistent with water dimers being the major contributor to the continuum. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by 0.75 W/m2 (which is about 1% of the total clear-sky absorption) by using these new measurements as compared to calculations with the MT_CKD-2.5 self-continuum model.

Origin of electronic absorption spectra of MLCT-excited and one-electron reduced 2,2′-bipyridine and 1,10-phenanthroline complexes

UV–Vis absorption spectra of one-electron reduction products and 3MLCT excited states of [ReICl(CO)3- (N,N)] (N,N = 2,20-bipyridine, bpy; 1,10-phenanthroline, phen) have been measured by low-temperature spectroelectrochemistry and UV–Vis transient absorption spectroscopy, respectively, and assigned by open-shell TD-DFT calculations. The characters of the electronic transitions are visualized and analyzed using electron density redistribution maps. It follows that reduced and excited states can be approximately formulated as [ReICl(CO)3(N,Nÿ)]ÿ and ⁄[ReIICl(CO)3(N,Nÿ)], respectively. UV–Vis spectra of the reduced complexes are dominated by IL transitions, plus weaker MLCT contributions. Excited-state spectra show an intense band in the UV region of 50% IL origin mixed with LMCT (bpy, 373 nm) or MLCT (phen, 307 nm) excitations. Because of the significant IL contribution, this spectral feature is akin to the principal IL band of the anions. In contrast, the excited-state visible spectral pattern arises from predominantly LMCT transitions, any resemblance with the reduced-state visible spectra being coincidental. The Re complexes studied herein are representatives of a broad class of metal a-diimines, for which similar spectroscopic behavior can be expected.

A preliminary investigation of the impact of catechol-O-methyltransferase genotype on the absorption and metabolism of green tea catechins

Purpose Green tea is thought to possess many beneficial effects on human health. However, the extent of green tea polyphenol biotransformation may affect its proposed therapeutic effects. Catechol-O-methyltransferase (COMT), the enzyme responsible for polyphenolic methylation, has a common polymorphism in the genetic code at position 158 reported to result in a 40% reduction in enzyme activity in in vitro studies. The current preliminary study was designed to investigate the impact of COMT genotype on green tea catechin absorption and metabolism in humans. Methods Twenty participants (10 of each homozygous COMT genotype) were recruited, and plasma concentration profiles were produced for epigallocatechin gallate (EGCG), epigallocatechin (EGC), epicatechin gallate (ECG), epicatechin (EC) and 4′-O-methyl EGCG after 1.1 g of Sunphenon decaffeinated green tea extract (836 mg green tea catechins), with a meal given after 60 min. Results For the entire group, EGCG, EGC, EC, ECG and 4′-O-methyl EGCG reached maximum concentrations of 1.09, 0.41, 0.33, 0.16 and 0.08 μM at 81.5, 98.5, 99.0, 85.5 and 96.5 min, respectively. Bimodal curves were observed for the non-gallated green tea catechins EGC and EC as opposed to single-peaked curves for the gallated green tea catechins EGCG and ECG. No significant parametric differences between COMT genotype groups were found. Conclusions In conclusion, the COMT Val(158/108)Met does not appear to have a dramatic influence on EGCG absorption and elimination. However, further pharmacokinetic research is needed to substantiate these findings.

Absorption and metabolism of olive oil secoiridoids in the small intestine

The secoiridoids 3,4-dihydroxyphenylethanol-elenolic acid (3,4-DHPEA-EA) and 3,4-dihydroxyphenylethanol-elenolic acid dialdehyde (3,4-DHPEA-EDA) account for approximately 55 % of the phenolic content of olive oil and may be partly responsible for its reported human health benefits. We have investigated the absorption and metabolism of these secoiridoids in the upper gastrointestinal tract. Both 3,4-DHPEA-EDA and 3,4-DHPEA-EA were relatively stable under gastric conditions, only undergoing limited hydrolysis. Both secoiridoids were transferred across a human cellular model of the small intestine (Caco-2 cells). However, no glucuronide conjugation was observed for either secoiridoid during transfer, although some hydroxytyrosol and homovanillic alcohol were formed. As Caco-2 cells are known to express only limited metabolic activity, we also investigated the absorption and metabolism of secoiridoids in isolated, perfused segments of the jejunum and ileum. Here, both secoiridoids underwent extensive metabolism, most notably a two-electron reduction and glucuronidation during the transfer across both the ileum and jejunum. Unlike Caco-2 cells, the intact small-intestinal segments contain NADPH-dependent aldo-keto reductases, which reduce the aldehyde carbonyl group of 3,4-DHPEA-EA and one of the two aldeydic carbonyl groups present on 3,4-DHPEA-EDA. These reduced forms are then glucuronidated and represent the major in vivo small-intestinal metabolites of the secoiridoids. In agreement with the cell studies, perfusion of the jejunum and ileum also yielded hydroxytyrosol and homovanillic alcohol and their respective glucuronides. We suggest that the reduced and glucuronidated forms represent novel physiological metabolites of the secoiridoids that should be pursued in vivo and investigated for their biological activity.

A functional coefficient model view of the Feldstein–Horioka puzzle

What does the saving–investment (SI) relation really measure and how should the SI relation be measured? These are two of the most discussed issues triggered by the so-called Feldstein–Horioka puzzle. Based on panel data we introduce a new variant of functional coefficient models that allows to separate long and short to medium run parameter dependence. The new modeling framework is applied to uncover the determinants of the SI relation. Macroeconomic state variables such as openness, the age dependency ratio, government current and consumption expenditures are found to affect the SI relation significantly in the long run.

A novel satellite mission concept for upper air water vapour, aerosol and cloud observations using integrated path differential absorption LiDAR limb sounding

We propose a new satellite mission to deliver high quality measurements of upper air water vapour. The concept centres around a LiDAR in limb sounding by occultation geometry, designed to operate as a very long path system for differential absorption measurements. We present a preliminary performance analysis with a system sized to send 75 mJ pulses at 25 Hz at four wavelengths close to 935 nm, to up to 5 microsatellites in a counter-rotating orbit, carrying retroreflectors characterized by a reflected beam divergence of roughly twice the emitted laser beam divergence of 15 µrad. This provides water vapour profiles with a vertical sampling of 110 m; preliminary calculations suggest that the system could detect concentrations of less than 5 ppm. A secondary payload of a fairly conventional medium resolution multispectral radiometer allows wide-swath cloud and aerosol imaging. The total weight and power of the system are estimated at 3 tons and 2,700 W respectively. This novel concept presents significant challenges, including the performance of the lasers in space, the tracking between the main spacecraft and the retroreflectors, the refractive effects of turbulence, and the design of the telescopes to achieve a high signal-to-noise ratio for the high precision measurements. The mission concept was conceived at the Alpbach Summer School 2010.

Spectrally invariant approximation within atmospheric radiative transfer

Certain algebraic combinations of single scattering albedo and solar radiation reflected from, or transmitted through, vegetation canopies do not vary with wavelength. These ‘‘spectrally invariant relationships’’ are the consequence of wavelength independence of the extinction coefficient and scattering phase function in veg- etation. In general, this wavelength independence does not hold in the atmosphere, but in cloud-dominated atmospheres the total extinction and total scattering phase function vary only weakly with wavelength. This paper identifies the atmospheric conditions under which the spectrally invariant approximation can accu- rately describe the extinction and scattering properties of cloudy atmospheres. The validity of the as- sumptions and the accuracy of the approximation are tested with 1D radiative transfer calculations using publicly available radiative transfer models: Discrete Ordinate Radiative Transfer (DISORT) and Santa Barbara DISORT Atmospheric Radiative Transfer (SBDART). It is shown for cloudy atmospheres with cloud optical depth above 3, and for spectral intervals that exclude strong water vapor absorption, that the spectrally invariant relationships found in vegetation canopy radiative transfer are valid to better than 5%. The physics behind this phenomenon, its mathematical basis, and possible applications to remote sensing and climate are discussed.

On spectral invariance of single scattering albedo for water droplets and ice crystals at weakly absorbing wavelengths

The single scattering albedo w_0l in atmospheric radiative transfer is the ratio of the scattering coefficient to the extinction coefficient. For cloud water droplets both the scattering and absorption coefficients, thus the single scattering albedo, are functions of wavelength l and droplet size r. This note shows that for water droplets at weakly absorbing wavelengths, the ratio w_0l(r)/w_0l(r0) of two single scattering albedo spectra is a linear function of w_0l(r). The slope and intercept of the linear function are wavelength independent and sum to unity. This relationship allows for a representation of any single scattering albedo spectrum w_0l(r) via one known spectrum w_0l(r0). We provide a simple physical explanation of the discovered relationship. Similar linear relationships were found for the single scattering albedo spectra of non-spherical ice crystals.

Catchment phosphorous losses: an export coefficient modelling approach with scenario analysis for water management

This paper presents the development of an export coefficient model to characterise the rates and sources of P export from land to water in four reservoir systems located in a semi-arid rural region in southern of Portugal. The model was developed to enable effective management of these important water resource systems under the EU Water Framework Directive. This is the first time such an approach has been fully adapted for the semi-arid systems typical of Mediterranean Europe. The sources of P loading delivered to each reservoir from its catchment were determined and scenario analysis was undertaken to predict the likely impact of catchment management strategies on the scale of rate of P loading delivered to each water body from its catchment. The results indicate the importance of farming and sewage treatment works/collective septic tanks discharges as the main contributors to the total diffuse and point source P loading delivered to the reservoirs, respectively. A reduction in the total P loading for all study areas would require control of farming practices and more efficient removal of P from human wastes prior to discharge to surface waters. The scenario analysis indicates a strategy based solely on reducing the agricultural P surplus may result in only a slow improvement in water quality, which would be unlikely to support the generation of good ecological status in reservoirs. The model application indicates that a reduction of P-inputs to the reservoirs should first focus on reducing P loading from sewage effluent discharges through the introduction of tertiary treatment (P-stripping) in all major residential areas. The fully calibrated export coefficient modelling approach transferred well to semi-arid regions, with the only significant limitation being the availability of suitable input data to drive the model. Further studies using this approach in semi-arid catchments are now needed to increase the knowledge of nutrient export behaviours in semi-arid regions.

Absolute high spectral resolution measurements of surface solar radiation for detection of water vapour continuum absorption

Solar-pointing Fourier transform infrared (FTIR) spectroscopy offers the capability to measure both the fine scale and broadband spectral structure of atmospheric transmission simultaneously across wide spectral regions. It is therefore suited to the study of both water vapour monomer and continuum absorption behaviours. However, in order to properly address this issue, it is necessary to radiatively calibrate the FTIR instrument response. A solar-pointing high-resolution FTIR spectrometer was deployed as part of the ‘Continuum Absorption by Visible and Infrared radiation and its Atmospheric Relevance’ (CAVIAR) consortium project. This paper describes the radiative calibration process using an ultra-high-temperature blackbody and the consideration of the related influence factors. The result is a radiatively calibrated measurement of the solar irradiation at the ground across the IR region from 2000 to 10 000 cm−1 with an uncertainty of between 3.3 and 5.9 per cent. This measurement is shown to be in good general agreement with a radiative-transfer model. The results from the CAVIAR field measurements are being used in ongoing studies of atmospheric absorbers, in particular the water vapour continuum.

Water vapour foreign-continuum absorption in near-infrared windows from laboratory measurements

For a long time, it has been believed that atmospheric absorption of radiation within wavelength regions of relatively high infrared transmittance (so-called ‘windows’) was dominated by the water vapour self-continuum, that is, spectrally smooth absorption caused by H2O−H2O pair interaction. Absorption due to the foreign continuum (i.e. caused mostly by H2O−N2 bimolecular absorption in the Earth's atmosphere) was considered to be negligible in the windows. We report new retrievals of the water vapour foreign continuum from high-resolution laboratory measurements at temperatures between 350 and 430 K in four near-infrared windows between 1.1 and 5 μm (9000–2000 cm−1). Our results indicate that the foreign continuum in these windows has a very weak temperature dependence and is typically between one and two orders of magnitude stronger than that given in representations of the continuum currently used in many climate and weather prediction models. This indicates that absorption owing to the foreign continuum may be comparable to the self-continuum under atmospheric conditions in the investigated windows. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by approximately 0.46 W m−2 (or 0.6% of the total clear-sky absorption) by using these new measurements when compared with calculations applying the widely used MTCKD (Mlawer–Tobin–Clough–Kneizys–Davies) foreign-continuum model.

Evaluation and management of the impact of land use change on the nitrogen and phosphorus load delivered to surface waters: the export coefficient modelling approach

A manageable, relatively inexpensive model was constructed to predict the loss of nitrogen and phosphorus from a complex catchment to its drainage system. The model used an export coefficient approach, calculating the total nitrogen (N) and total phosphorus (P) load delivered annually to a water body as the sum of the individual loads exported from each nutrient source in its catchment. The export coefficient modelling approach permits scaling up from plot-scale experiments to the catchment scale, allowing application of findings from field experimental studies at a suitable scale for catchment management. The catchment of the River Windrush, a tributary of the River Thames, UK, was selected as the initial study site. The Windrush model predicted nitrogen and phosphorus loading within 2% of observed total nitrogen load and 0.5% of observed total phosphorus load in 1989. The export coefficient modelling approach was then validated by application in a second research basin, the catchment of Slapton Ley, south Devon, which has markedly different catchment hydrology and land use. The Slapton model was calibrated within 2% of observed total nitrogen load and 2.5% of observed total phosphorus load in 1986. Both models proved sensitive to the impact of temporal changes in land use and management on water quality in both catchments, and were therefore used to evaluate the potential impact of proposed pollution control strategies on the nutrient loading delivered to the River Windrush and Slapton Ley

The Natural History of Slapton Ley Nature Reserve XVIII: nitrogen and phosphorus losses from the catchment - an export coefficient modelling approach

Nitrogen and phosphorus losses from the catchment of Slapton Ley, a small coastal lake in SW England, were calculated using an adaptation of a model developed by Jorgensen (1980). A detailed survey of the catchment revealed that its land use is dominated by both permanent and temporary grassland (respectively 38 and 32% of its total area), and that the remainder is made up of the cultivation of cereals and field vegetables, and market gardening. Livestock numbers in the catchment constitute ca. 6600 head of cattle, 10,000 sheep, 590 pigs, 1700 poultry and 58 horses. The permanent human population of the area is ca. 2000, served by two small gravity-fed sewage treatment works (STWs). Inputs to, and losses from, farmland in the catchment were computed using Jorgensen’s model, and coefficients derived from the data of Cooke (1976), Gostick (1982), Rast and Lee (1983) and Vollenweider (1968). Allowing for outputs from STWs, the total annual external load of N and P upon Slapton Ley is 160 t (35 kg ha-1) a-1 N, and 4.8 t (1.05 kg ha-1) a-1 P. Accordingly to Vollenweider (1968, 1975), such loadings exceed OECD permissible level by a factor of ca. 50 in the case of N, and ca. 5 in that of P. In order to reduce nutrient loads, attention would need to be paid to both STW and agricultural sources.