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 model for exchange rates with crawling bands: an application to the Colombian peso

This paper builds upon previous research on currency bands, and provides a model for the Colombian peso. Stochastic differential equations are combined with information related to the Colombian currency band to estimate competing models of the behaviour of the Colombian peso within the limits of the currency band. The resulting moments of the density function for the simulated returns describe adequately most of the characteristics of the sample returns data. The factor included to account for the intra-marginal intervention performed to drive the rate towards the Central Parity accounts only for 6.5% of the daily change, which supports the argument that intervention, if performed by the Central Bank, it is not directed to push the currency towards the limits. Moreover, the credibility of the Colombian Central Bank, Banco de la República’s ability to defend the band seems low.

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.

Temporal-envelope constancy of speech in rooms and the perceptual weighting of frequency bands

Three experiments measured constancy in speech perception, using natural-speech messages or noise-band vocoder versions of them. The eight vocoder-bands had equally log-spaced center-frequencies and the shapes of corresponding “auditory” filters. Consequently, the bands had the temporal envelopes that arise in these auditory filters when the speech is played. The “sir” or “stir” test-words were distinguished by degrees of amplitude modulation, and played in the context; “next you’ll get _ to click on.” Listeners identified test-words appropriately, even in the vocoder conditions where the speech had a “noise-like” quality. Constancy was assessed by comparing the identification of test-words with low or high levels of room reflections across conditions where the context had either a low or a high level of reflections. Constancy was obtained with both the natural and the vocoded speech, indicating that the effect arises through temporal-envelope processing. Two further experiments assessed perceptual weighting of the different bands, both in the test word and in the context. The resulting weighting functions both increase monotonically with frequency, following the spectral characteristics of the test-word’s [s]. It is suggested that these two weighting functions are similar because they both come about through the perceptual grouping of the test-word’s bands.

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.

The water vapour continuum: brief history and recent developments

The water vapour continuum is characterised by absorption that varies smoothly with wavelength, from the visible to the microwave. It is present within the rotational and vibrational–rotational bands of water vapour, which consist of large numbers of narrow spectral lines, and in the many ‘windows’ between these bands. The continuum absorption in the window regions is of particular importance for the Earth’s radiation budget and for remote-sensing techniques that exploit these windows. Historically, most attention has focused on the 8–12 μm (mid-infrared) atmospheric window, where the continuum is relatively well-characterised, but there have been many fewer measurements within bands and in other window regions. In addition, the causes of the continuum remain a subject of controversy. This paper provides a brief historical overview of the development of understanding of the continuum and then reviews recent developments, with a focus on the near-infrared spectral region. Recent laboratory measurements in near-infrared windows, which reveal absorption typically an order of magnitude stronger than in widely used continuum models, are shown to have important consequences for remote-sensing techniques that use these windows for retrieving cloud properties.

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.

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.

Cloud bands over southern Africa: seasonality, contribution to rainfall variability, and modulation by the MJO

Tropical-extratropical cloud band systems over southern Africa, known as tropical temperate troughs (TTTs), are known to contribute substantially to South African summer rainfall. This study performs a comprehensive assessment of the seasonal cycle and rainfall contribution of TTTs by using a novel object-based strategy that explicitly tracks these systems for their full life cycle. The methodology incorporates a simple assignment of station rainfall data to each event, thereby creating a database containing detailed rainfall characteristics for each TTT. This is used to explore the importance of TTTs for rain days and climatological rainfall totals in October–March. Average contributions range from 30 to 60 % with substantial spatial heterogeneity observed. TTT rainfall contributions over the Highveld and eastern escarpment are lower than expected. A short analysis of TTT rainfall variability indicates TTTs provide substantial, but not dominant, intraseasonal and interannual variability in station rainfall totals. TTTs are however responsible for a high proportion of heavy rainfall days. Of 52 extreme rainfall events in the 1979–1999 period, 30 are associated with these tropical-extratropical interactions. Cut-off lows were included in the evolution of 6 of these TTTs. The study concludes with an analysis of the question: does the Madden-Julian Oscillation influence the intensity of TTT rainfall over South Africa? Results suggest a weak but significant suppression (enhancement) of intensity during phase 1(6).

Near-infrared water vapour self-continuum at close to room temperature

The gaseous absorption of solar radiation within near-infrared atmospheric windows in the Earth's atmosphere is dominated by the water vapour continuum. Recent measurements by Baranov et al. (2011) [17] in 2500 cm−1 (4 μm) window and by Ptashnik et al. (2011) [18] in a few near-infrared windows revealed that the self-continuum absorption is typically an order of magnitude stronger than given by the MT_CKD continuum model prior to version 2.5. Most of these measurements, however, were made at elevated temperatures, which makes their application to atmospheric conditions difficult. Here we report new laboratory measurements of the self-continuum absorption at 289 and 318 K in the near-infrared spectral region 1300–8000 cm−1, using a multipass 30 m base cell with total optical path 612 m. Our results confirm the main conclusions of the previous measurements both within bands and in windows. Of particular note is that we present what we believe to be the first near-room temperature measurement using Fourier Transform Spectrometry of the self-continuum in the 6200 cm−1 (1.6 μm) window, which provides tentative evidence that, at such temperatures, the water vapour continuum absorption may be as strong as it is in 2.1 μm and 4 μm windows and up to 2 orders of magnitude stronger than the MT_CKD-2.5 continuum. We note that alternative methods of measuring the continuum in this window have yielded widely differing assessment of its strength, which emphasises the need for further measurements.

The global distribution of phytoplankton size spectrum and size classes from their light-absorption spectra derived from satellite data

The absorption spectra of phytoplankton in the visible domain hold implicit information on the phytoplankton community structure. Here we use this information to retrieve quantitative information on phytoplankton size structure by developing a novel method to compute the exponent of an assumed power-law for their particle-size spectrum. This quantity, in combination with total chlorophyll-a concentration, can be used to estimate the fractional concentration of chlorophyll in any arbitrarily-defined size class of phytoplankton. We further define and derive expressions for two distinct measures of cell size of mixed populations, namely, the average spherical diameter of a bio-optically equivalent homogeneous population of cells of equal size, and the average equivalent spherical diameter of a population of cells that follow a power-law particle-size distribution. The method relies on measurements of two quantities of a phytoplankton sample: the concentration of chlorophyll-a, which is an operational index of phytoplankton biomass, and the total absorption coefficient of phytoplankton in the red peak of visible spectrum at 676 nm. A sensitivity analysis confirms that the relative errors in the estimates of the exponent of particle size spectra are reasonably low. The exponents of phytoplankton size spectra, estimated for a large set of in situ data from a variety of oceanic environments (~ 2400 samples), are within a reasonable range; and the estimated fractions of chlorophyll in pico-, nano- and micro-phytoplankton are generally consistent with those obtained by an independent, indirect method based on diagnostic pigments determined using high-performance liquid chromatography. The estimates of cell size for in situ samples dominated by different phytoplankton types (diatoms, prymnesiophytes, Prochlorococcus, other cyanobacteria and green algae) yield nominal sizes consistent with the taxonomic classification. To estimate the same quantities from satellite-derived ocean-colour data, we combine our method with algorithms for obtaining inherent optical properties from remote sensing. The spatial distribution of the size-spectrum exponent and the chlorophyll fractions of pico-, nano- and micro-phytoplankton estimated from satellite remote sensing are in agreement with the current understanding of the biogeography of phytoplankton functional types in the global oceans. This study contributes to our understanding of the distribution and time evolution of phytoplankton size structure in the global oceans.

Modeling ocean primary production: sensitivity to spectral resolution of attenuation and absorption of light

Modeling the vertical penetration of photosynthetically active radiation (PAR) through the ocean, and its utilization by phytoplankton, is fundamental to simulating marine primary production. The variation of attenuation and absorption of light with wavelength suggests that photosynthesis should be modeled at high spectral resolution, but this is computationally expensive. To model primary production in global 3d models, a balance between computer time and accuracy is necessary. We investigate the effects of varying the spectral resolution of the underwater light field and the photosynthetic efficiency of phytoplankton (α∗), on primary production using a 1d coupled ecosystem ocean turbulence model. The model is applied at three sites in the Atlantic Ocean (CIS (∼60°N), PAP (∼50°N) and ESTOC (∼30°N)) to include the effect of different meteorological forcing and parameter sets. We also investigate three different methods for modeling α∗ – as a fixed constant, varying with both wavelength and chlorophyll concentration [Bricaud, A., Morel, A., Babin, M., Allali, K., Claustre, H., 1998. Variations of light absorption by suspended particles with chlorophyll a concentration in oceanic (case 1) waters. Analysis and implications for bio-optical models. J. Geophys. Res. 103, 31033–31044], and using a non-spectral parameterization [Anderson, T.R., 1993. A spectrally averaged model of light penetration and photosynthesis. Limnol. Oceanogr. 38, 1403–1419]. After selecting the appropriate ecosystem parameters for each of the three sites we vary the spectral resolution of light and α∗ from 1 to 61 wavebands and study the results in conjunction with the three different α∗ estimation methods. The results show modeled estimates of ocean primary productivity are highly sensitive to the degree of spectral resolution and α∗. For accurate simulations of primary production and chlorophyll distribution we recommend a spectral resolution of at least six wavebands if α∗ is a function of wavelength and chlorophyll, and three wavebands if α∗ is a fixed value.

Aerosol absorption over the clear-sky oceans deduced from POLDER-1 and AERONET observations

We estimate aerosol absorption over the clear-sky oceans using aerosol geophysical products from POLDER-1 space measurements and absorption properties from ground-based AERONET measurements. Our best estimate is 2.5 Wm-2 averaged over the 8-month lifetime of POLDER-1. Low and high absorption estimates are 2.2 and 3.1 Wm-2 based on the variability in aerosol single scattering albedo observed by AERONET. Main sources of uncertainties are the discrimation of the aerosol type from satellite measurements, and potential clear-sky bias induced by the cloud-screening procedure.