Palaeohydrology of the Fazzan Basin and surrounding regions: The last 7 million years

We have integrated information on topography, geology and geomorphology with the results of targeted fieldwork in order to develop a chronology for the development of Lake Megafazzan, a giant lake that has periodically existed in the Fazzan Basin since the late Miocene. The development of the basin can be best understood by considering the main geological and geomorphological events that occurred thought Libya during this period and thus an overview of the palaeohydrology of all Libya is also presented. The origin of the Fazzan Basin appears to lie in the Late Miocene. At this time Libya was dominated by two large rivers systems that flowed into the Mediterranean Sea, the Sahabi River draining central and eastern Libya and the Wadi Nashu River draining much of western Libya. As the Miocene progressed the region become increasingly affected by volcanic activity on its northern and eastern margin that appears to have blocked the River Nashu in Late Miocene or early Messinian times forming a sizeable closed basin in the Fazzan within which proto-Lake Megafazzan would have developed during humid periods. The fall in base level associated with the Messinian desiccation of the Mediterranean Sea promoted down-cutting and extension of river systems throughout much of Libya. To the south of the proto Fazzan Basin the Sahabi River tributary know as Wadi Barjuj appears to have expanded its headwaters westwards. The channel now terminates at Al Haruj al Aswad. We interpret this as a suggestion that Wadi Barjuj was blocked by the progressive development of Al Haruj al Aswad. K/Ar dating of lava flows suggests that this occurred between 4 and 2 Ma. This event would have increased the size of the closed basin in the Fazzan by about half, producing a catchment close to its current size (-350,000 km(2)). The Fazzan Basin contains a wealth of Pleistocene to recent palaeolake sediment outcrops and shorelines. Dating of these features demonstrates evidence of lacustrine conditions during numerous interglacials spanning a period greater than 420 ka. The middle to late Pleistocene interglacials were humid enough to produce a giant lake of about 135,000 km(2) that we have called Lake Megafazzan. Later lake phases were smaller, the interglacials less humid, developing lakes of a few thousand square kilometres. In parallel with these palaeohydrological developments in the Fazzan Basin, change was occurring in other parts of Libya. The Lower Pliocene sea level rise caused sediments to infill much of the Messinian channel system. As this was occurring, subsidence in the Al Kufrah Basin caused expansion of the Al Kufrah River system at the expense of the River Sahabi. By the Pleistocene, the Al Kufrah River dominated the palaeohydrology of eastern Libya and had developed a very large inland delta in its northern reaches that exhibited a complex distributary channel network which at times fed substantial lakes in the Sirt Basin. At this time Libya was a veritable lake district during humid periods with about 10% of the country underwater. (C) 2008 Elsevier B.V. All rights reserved.

Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp′]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp′=Cp; L2=dppe; Cp′=Cp∗)

A series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(C CAr)(L-2)Cp'] (Ar = phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2 = (PPh3)(2), Cp' = Cp; L-2 = dppe; Cp' = Cp*) have been examined using electrochemical and spectroelectrochemical methods. One-electron oxidation of these complexes gave the corresponding radical cations [Ru(C CAr)(L2)Cp'](+). Those cations based on Ru(dppe)Cp*, or which feature a para-tolyl acetylide substituent, are more chemically robust than examples featuring the Ru(PPh3)(2)Cp moiety, permitting good quality UV-Vis-NIR and IR spectroscopic data to be obtained using spectroelectrochemical methods. On the basis of TD DFT calculations, the low energy (NIR) absorption bands in the experimental electronic spectra for most of these radical cations are assigned to transitions between the beta-HOSO and beta-LUSO, both of which have appreciable metal d and ethynyl pi character. However, the large contribution from the anthryl moiety to the frontier orbitals of [Ru(C CC14H9)(L2)CP'](+) suggests compounds containing this moiety should be described as metal-stabilised anthryl radical cations.

Can carbon surface oxidation shift the pore size distribution curve calculated from Ar, N(2) and CO(2) adsorption isotherms? Simulation results for a realistic carbon model

Using the virtual porous carbon model proposed by Harris et al, we study the effect of carbon surface oxidation on the pore size distribution (PSD) curve determined from simulated Ar, N(2) and CO(2) isotherms. It is assumed that surface oxidation is not destructive for the carbon skeleton, and that all pores are accessible for studied molecules (i.e., only the effect of the change of surface chemical composition is studied). The results obtained show two important things, i.e., oxidation of the carbon surface very slightly changes the absolute porosity (calculated from the geometric method of Bhattacharya and Gubbins (BG)); however, PSD curves calculated from simulated isotherms are to a greater or lesser extent affected by the presence of surface oxides. The most reliable results are obtained from Ar adsorption data. Not only is adsorption of this adsorbate practically independent from the presence of surface oxides, but, more importantly, for this molecule one can apply the slit-like model of pores as the first approach to recover the average pore diameter of a real carbon structure. For nitrogen, the effect of carbon surface chemical composition is observed due to the quadrupole moment of this molecule, and this effect shifts the PSD curves compared to Ar. The largest differences are seen for CO2, and it is clearly demonstrated that the PSD curves obtained from adsorption isotherms of this molecule contain artificial peaks and the average pore diameter is strongly influenced by the presence of electrostatic adsorbate-adsorbate as well as adsorbate-adsorbent interactions.

Hyper-parallel tempering Monte Carlo simulations of Ar adsorption in new models of microporous non-graphitizing activated carbon: effect of microporosity

The adsorption of gases on microporous carbons is still poorly understood, partly because the structure of these carbons is not well known. Here, a model of microporous carbons based on fullerene- like fragments is used as the basis for a theoretical study of Ar adsorption on carbon. First, a simulation box was constructed, containing a plausible arrangement of carbon fragments. Next, using a new Monte Carlo simulation algorithm, two types of carbon fragments were gradually placed into the initial structure to increase its microporosity. Thirty six different microporous carbon structures were generated in this way. Using the method proposed recently by Bhattacharya and Gubbins ( BG), the micropore size distributions of the obtained carbon models and the average micropore diameters were calculated. For ten chosen structures, Ar adsorption isotherms ( 87 K) were simulated via the hyper- parallel tempering Monte Carlo simulation method. The isotherms obtained in this way were described by widely applied methods of microporous carbon characterisation, i. e. Nguyen and Do, Horvath - Kawazoe, high- resolution alpha(a)s plots, adsorption potential distributions and the Dubinin - Astakhov ( DA) equation. From simulated isotherms described by the DA equation, the average micropore diameters were calculated using empirical relationships proposed by different authors and they were compared with those from the BG method.