Size parameters, size-class distribution and area-number relationship of microscopic charcoal: relevance for fire reconstruction

Charcoal analysis was conducted on sediment cores from three lakes to assess the relationship between the area and number of charcoal particles. Three charcoal-size parameters (maximum breadth, maximum length and area) were measured on sediment samples representing various vegetation types, including shrub tundra, boreal forest and temperate forest. These parameters and charcoal size-class distributions do not differ statistically between two sites where the same preparation technique (glycerine pollen slides) was used, but they differ for the same core when different techniques were applied. Results suggest that differences in charcoal size and size-class distribution are mainly caused by different preparation techniques and are not related to vegetation-type variation. At all three sites, the area and number concentrations of charcoal particles are highly correlated in standard pollen slides; 82–83% of the variability of the charcoal-area concentration can be explained by the particle-number concentration. Comparisons between predicted and measured area concentrations show that regression equations linking charcoal number and area concentrations can be used across sites as long as the same pollen-preparation technique is used. Thus it is concluded that it is unnecessary to measure charcoal areas in standard pollen slides – a time-consuming and tedious process.

Chromium uptake and adsorption in marine phytoplankton - Implications for the marine chromium cycle

Using the radioisotope 51Cr, we investigated the controls of cellular Cr accumulation in an array of marine phytoplankton grown in environmentally relevant Cr concentrations (1–10 nM). Given the affinity of Cr(III) for amorphous Fe-hydroxide mineral surfaces, and the formation of these mineral phases on the outside of phytoplankton cells, extracellular Cr was monitored in a model diatom species (Thalassiosira weissflogii) as extracellular Fe concentrations varied. Extracellular Cr in T. weissflogii increased with increasing extracellular Fe, demonstrating that Cr may be removed from seawater via extracellular adsorption to phytoplankton. Short-term Cr(VI) and Cr(III) uptake experiments performed with T. weissflogii demonstrated that Cr(III) was the primary oxidation state adsorbing to cells and being internalized by them. Cellular Cr:C ratios (<0.5 μmol Cr mol C−1) of the eight phytoplankton species surveyed were significantly lower than previously reported Cr:C ratios in marine particles with a high biogenic component (10–300 μmol Cr mol C−1). This indicates that Cr(III) likely accumulates in marine particles due to uptake and/or adsorption. Mass balance calculations demonstrate that surface water Cr deficits can be explained via loss of Cr(III) to exported particles, thereby providing a mechanism to account for the nutrient depth profile for Cr in modern seawater. Given the large fractionation of stable Cr isotopes during Cr(VI) reduction, Cr(III) associated with exported organic carbon is likely enriched in lighter isotopes. Most sedimentary Cr isotope studies have thus far neglected internal fractionating processes in the marine Cr cycle, but our data indicate that loss of Cr to exported particles may be traced in the sedimentary d53Cr record.

Processing and adsorption control in ZnO single nanowire photodetectors

ZnO single nanowire photodetectors have been measured in different ambient conditions in order to understand and control adsorption processes on the surface. A decrease in the conductivity has been observed as a function of time when the nanowires are exposed to air, due to adsorbed O2/H2O species at the nanowire surface. In order to have a device with stable characteristics in time, thermal desorption has been used to recover the original conductivity followed by PMMA coating of the exposed nanowire surface.

Glycerin and lecithin inclusion in diets for brown egg-layinghens: Effects on egg production and nutrient digestibility

The effects of the inclusion of raw glycerin (GLYC) and lecithin in the diet on egg production,egg quality and total tract apparent retention (TTAR) of dietary components was studied inbrown egg-laying hens from 23 to 51 wk of age. The experimental design was completelyrandomized with six diets combined as a 2 × 3 factorial with two levels of GLYC (0 vs.70 g/kg) and three animal fat to lecithin ratios (40:0, 20:20 and 0:40 g/kg). Each treatmentwas replicated eight times and the experimental unit was a cage with ten hens. Productionwas recorded by replicate every 28-d period and cumulatively. For the entire experiment,the inclusion of GLYC in the diet hindered feed conversion ratio per kilogram of eggs (2.071vs. 2.039; P < 0.05) but did not affect any of the other production or egg quality traits studied.The replacement of animal fat by lecithin (40:0, 20:20 and 0:40 g/kg) increased egg weight(60.1, 60.7 and 61.8 g, respectively; P < 0.001) and egg mass production (56.8, 57.5 and58.8 g/d, respectively; P < 0.01) and improved yolk color as measured by the DSM colorfan (9.2, 9.2 and 9.5, respectively; P < 0.001) and feed conversion ratio per kilogram of eggs(2.072, 2.068 and 2.027, respectively; P < 0.05). Feed intake, egg production and body weightgain, however, were not affected. The inclusion of GLYC in the diet did not affect nutrientretention but lecithin inclusion improved TTAR of dry matter (P < 0.05), organic matter(P < 0.05), ether extract (P < 0.001) and gross energy (P < 0.001). In summary, the inclusionof 70 g glycerol/kg diet hindered feed conversion ratio per kilogram of eggs but did notaffect any other production or digestibility trait. The replacement of animal fat by lecithinimproved egg weight, egg yolk color and nutrient digestibility. Consequently, lecithin canbe used as a lipid source in laying hen diets with beneficial effects on egg production

Influence of glycerin and lecithin inclusion in the diet on liver characteristics and lipid fraction in the serum of brownegg laying hens at 55 week of age

The effects of the inclusion of raw glycerin (GLYC) and raw lecithin, in the diet (23 to 55 wk) on liver characteristics and various serum lipid fractions were studied in brown egg-laying hens at 55 wk of age. The control diets were based on corn, soybean meal, and 4% supplemental fat and contained 2,750 kcal AMEn/kg, 16.5% CP, and 0.73% digestible Lys. The diets were arranged as a 2 × 3 factorial with 2 levels of GLYC (0 and 7%) and 3 animal fat to lecithin ratios (4:0, 2:2, and 0:4%). Each treatment was replicated 8 times and the experimental unit was a cage with 10 hens. At 55 wk of age, 2 hens per cage replicate were randomly selected, weighed individually, and slaughtered by CO2 inhalation. Liver was immediately removed and weighed and the color recorded by spectrophotometry. In addition, blood samples from one bird per replicate were collected from the wing vein and the concentration of total cholesterol, low and high density lipoprotein cholesterol, and triglycerides were determined. The data were analyzed as a completely randomized design and the main effects of GLYC and lecithin content of the diet and the interactions were determined. No interactions between GLYC and lecithin content of the diets were detected for any of the variables studied. Liver characteristics and serum lipid traits were not affected by the inclusion of GLYC in the diet. The substitution of animal fat by lecithin, however, reduced the redness (a* 14.9 to 13.8) and yellowness (b* 8.60 to 7.20) values of the liver (P < 0.05) but did not affect the content of serum lipid fractions. It is concluded that the inclusion of GLYC and lecithin in the diet did not affect liver size or serum lipid fraction. However, the inclusion of lecithin reduced the a* and b* value of the liver

Assessment of CO2 adsorption capacity on activated carbons by a combination of batch and dynamic tests

In this work, batch and dynamic adsorption tests are coupled for an accurate evaluation of CO2 adsorption performance for three different activated carbons obtained from olives stones by chemical activation followed by physical activation with CO2 at varying times, i.e. 20, 40 and 60 h. Kinetic and thermodynamic CO2 adsorption tests from simulated flue-gas at different temperature and CO2 pressure are carried out both in batch (a manometric equipment operating with pure CO2) and dynamic (a lab-scale fixed-bed column operating with CO2/N2 mixture) conditions. The textural characterization of the activated carbon samples shows a direct dependence of both micropore and ultramicropore volume on the activation time, hence AC60 has the higher contribution. The adsorption tests conducted at 273 and 293 K showed that, when CO2 pressure is lower than 0.3 bar, the lower the activation time the higher CO2 adsorption capacity and a ranking ωeq(AC20)>ωeq(AC40)>ωeq(AC60) can be exactly defined when T= 293 K. This result can be likely ascribed to a narrower pore size distribution of the AC20 sample, whose smaller pores are more effective for CO2 capture at higher temperature and lower CO2 pressure, the latter representing operating conditions of major interest for decarbonation of a flue-gas effluent. Moreover, the experimental results obtained from dynamic tests confirm the results derived from the batch tests in terms of CO2 adsorption capacity. It is important to highlight that the adsorption of N2 on the synthesized AC samples can be considered negligible. Finally, the importance of a proper analysis of characterization data and adsorption experimental results is highlighted for a correct assessment of CO2 removal performances of activated carbons at different CO2 pressure and operating temperature.

Use of Eutectic Mixtures for Preparation of Monolithic Carbons with CO2-Adsorption and Gas-Separation Capabilities

With global warming becoming one of the main problems our society is facing nowadays, there is an urgent demand to develop materials suitable for CO2 storage as well as for gas separation. Within this context, hierarchical porous structures are of great interest for in-flow applications because of the desirable combination of an extensive internal reactive surface along narrow nanopores with facile molecular transport through broad “highways” leading to and from these pores. Deep eutectic solvents (DESs) have been recently used in the synthesis of carbon monoliths exhibiting a bicontinuous porous structure composed of continuous macroporous channels and a continuous carbon network that contains a certain microporosity and provides considerable surface area. In this work, we have prepared two DESs for the preparation of two hierarchical carbon monoliths with different compositions (e.g., either nitrogen-doped or not) and structure. It is worth noting that DESs played a capital role in the synthesis of hierarchical carbon monoliths not only promoting the spinodal decomposition that governs the formation of the bicontinuous porous structure but also providing the precursors required to tailor the composition and the molecular sieve structure of the resulting carbons. We have studied the performance of these two carbons for CO2, N2, and CH4 adsorption in both monolithic and powdered form. We have also studied the selective adsorption of CO2 versus CH4 in equilibrium and dynamic conditions. We found that these materials combined a high CO2-sorption capacity besides an excellent CO2/N2 and CO2/CH4 selectivity and, interestingly, this performance was preserved when processed in both monolithic and powdered form.

Effects of potential models on the adsorption of ethane and ethylene on graphitized thermal carbon black. Study of two-dimensional critical temperature and isosteric heat versus loading

Adsorption of ethylene and ethane on graphitized thermal carbon black and in slit pores whose walls are composed of graphene layers is studied in detail to investigate the packing efficiency, the two-dimensional critical temperature, and the variation of the isosteric heat of adsorption with loading and temperature. Here we used a Monte Carlo simulation method with a grand canonical Monte Carlo ensemble. A number of two-center Lennard-Jones (LJ) potential models are investigated to study the impact of the choice of potential models in the description of adsorption behavior. We chose two 2C-LJ potential models in our investigation of the (i) UA-TraPPE-LJ model of Martin and Siepmann (J. Phys. Chem. B 1998,102, 25692577) for ethane and Wick et al. (J. Phys. Chem. B 2000,104, 8008-8016) for ethylene and (ii) AUA4-LJ model of Ungerer et al. (J. Chem. Phys. 2000,112, 5499-5510) for ethane and Bourasseau et al. (J. Chem. Phys. 2003, 118, 3020-3034) for ethylene. These models are used to study the adsorption of ethane and ethylene on graphitized thermal carbon black. It is found that the solid-fluid binary interaction parameter is a function of adsorbate and temperature, and the adsorption isotherms and heat of adsorption are well described by both the UA-TraPPE and AUA models, although the UA-TraPPE model performs slightly better. However, the local distributions predicted by these two models are slightly different. These two models are used to explore the two-dimensional condensation for the graphitized thermal carbon black, and these values are 110 K for ethylene and 120 K for ethane.

Application of density functional theory to equilibrium adsorption of argon and nitrogen on amorphous silica surface

We present a new version of non-local density functional theory (NL-DFT) adapted to description of vapor adsorption isotherms on amorphous materials like non-porous silica. The novel feature of this approach is that it accounts for the roughness of adsorbent surface. The solid–fluid interaction is described in the same framework as in the case of fluid–fluid interactions, using the Weeks–Chandler–Andersen (WCA) scheme and the Carnahan–Starling (CS) equation for attractive and repulsive parts of the Helmholtz free energy, respectively. Application to nitrogen and argon adsorption isotherms on non-porous silica LiChrospher Si-1000 at their boiling points, recently published by Jaroniec and co-workers, has shown an excellent correlative ability of our approach over the complete range of pressures, which suggests that the surface roughness is mostly the reason for the observed behavior of adsorption isotherms. From the analysis of these data, we found that in the case of nitrogen adsorption short-range interactions between oxygen atoms on the silica surface and quadrupole of nitrogen molecules play an important role. The approach presented in this paper may be further used in quantitative analysis of adsorption and desorption isotherms in cylindrical pores such as MCM-41 and carbon nanotubes.

Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid–fluid molecular parameters for the system amorphous silica–Ar and amorphous silica–N2, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.

Adsorption of N-2, Ar, acetone, chloroform and acetone-chloroform mixture on carbon black in the framework of molecular layer structure theory (MLST)

Adsorption of pure nitrogen, argon, acetone, chloroform and acetone-chloroform mixture on graphitized thermal carbon black is considered at sub-critical conditions by means of molecular layer structure theory (MLST). In the present version of the MLST an adsorbed fluid is considered as a sequence of 2D molecular layers, whose Helmholtz free energies are obtained directly from the analysis of experimental adsorption isotherm of pure components. The interaction of the nearest layers is accounted for in the framework of mean field approximation. This approach allows quantitative correlating of experimental nitrogen and argon adsorption isotherm both in the monolayer region and in the range of multi-layer coverage up to 10 molecular layers. In the case of acetone and chloroform the approach also leads to excellent quantitative correlation of adsorption isotherms, while molecular approaches such as the non-local density functional theory (NLDFT) fail to describe those isotherms. We extend our new method to calculate the Helmholtz free energy of an adsorbed mixture using a simple mixing rule, and this allows us to predict mixture adsorption isotherms from pure component adsorption isotherms. The approach, which accounts for the difference in composition in different molecular layers, is tested against the experimental data of acetone-chloroform mixture (non-ideal mixture) adsorption on graphitized thermal carbon black at 50 degrees C. (C) 2005 Elsevier Ltd. All rights reserved.

Estimation of adsorption capacity for dissociating and non dissociating aromatic compounds on activated carbon with different models

The process of adsorption of two dissociating and two non-dissociating aromatic compounds from dilute aqueous solutions on an untreated commercially available activated carbon (B.D.H.) was investigated systematically. All adsorption experiments were carried out in pH controlled aqueous solutions. The experimental isotherms were fitted into four different models (Langmuir homogenous Models, Langmuir binary Model, Langmuir-Freundlich single model and Langmuir-Freundlich double model). Variation of the model parameters with the solution pH was studied and used to gain further insight into the adsorption process. The relationship between the model parameters and the solution pH and pK(a) was used to predict the adsorption capacity in molecular and ionic form of solutes in other solution. A relationship was sought to predict the effect of pH on the adsorption systems and for estimating the maximum adsorption capacity of carbon at any pH where the solute is ionized reasonably well. N-2 and CO2 adsorption were used to characterize the carbon. X-ray Photoelectron Spectroscopy (XPS) measurement was used for surface elemental analysis of the activated carbon.

Equilibrium adsorption in cylindrical mesopores: A modified Broekhoff and de boer theory versus density functional theory

This paper presents a thermodynamic analysis of capillary condensation phenomena in cylindrical pores. Here, we modified the Broekhoff and de Boer (BdB) model for cylindrical pores accounting for the effect of the pore radius on the potential exerted by the pore walls. The new approach incorporates the recently published standard nitrogen and argon adsorption isotherm on nonporous silica LiChrospher Si-1000. The developed model is tested against the nonlocal density functional theory (NLDFT), and the criterion for this comparison is the condensation/evaporation pressure versus the pore diameter. The quantitative agreement between the NLDFT and the refined version of the BdB theory is ascertained for pores larger than 2 nm. The modified BdB theory was applied to the experimental adsorption branch of adsorption isotherms of a number of MCM-41 samples to determine their pore size distributions (PSDs). It was found that the PSDs determined with the new BdB approach coincide with those determined with the NLDFT (also using the experimental adsorption branch). As opposed to the NLDFT, the modified BdB theory is very simple in its utilization and therefore can be used as a convenient tool to obtain PSDs of all mesoporous solids from the analysis of the adsorption branch of adsorption isotherms of any subcritical fluids.

Modeling of adsorption on nongraphitized carbon surface: GCMC simulation studies and comparison with experimental data

We model nongraphitized carbon black surfaces and investigate adsorption of argon on these surfaces by using the grand canonical Monte Carlo simulation. In this model, the nongraphitized surface is modeled as a stack of graphene layers with some carbon atoms of the top graphene layer being randomly removed. The percentage of the surface carbon atoms being removed and the effective size of the defect ( created by the removal) are the key parameters to characterize the nongraphitized surface. The patterns of adsorption isotherm and isosteric heat are particularly studied, as a function of these surface parameters as well as pressure and temperature. It is shown that the adsorption isotherm shows a steplike behavior on a perfect graphite surface and becomes smoother on nongraphitized surfaces. Regarding the isosteric heat versus loading, we observe for the case of graphitized thermal carbon black the increase of heat in the submonolayer coverage and then a sharp decline in the heat when the second layer is starting to form, beyond which it increases slightly. On the other hand, the isosteric heat versus loading for a highly nongraphitized surface shows a general decline with respect to loading, which is due to the energetic heterogeneity of the surface. It is only when the fluid-fluid interaction is greater than the surface energetic factor that we see a minimum-maximum in the isosteric heat versus loading. These simulation results of isosteric heat agree well with the experimental results of graphitization of Spheron 6 (Polley, M. H.; Schaeffer, W. D.; Smith, W. R. J. Phys. Chem. 1953, 57, 469; Beebe, R. A.; Young, D. M. J. Phys. Chem. 1954, 58, 93). Adsorption isotherms and isosteric heat in pores whose walls have defects are also studied from the simulation, and the pattern of isotherm and isosteric heat could be used to identify the fingerprint of the surface.

Adsorption in slit pores and pore-size distribution: A molecular layer structure theory

A new approach is developed to analyze the thermodynamic properties of a sub-critical fluid adsorbed in a slit pore of activated carbon. The approach is based on a representation that an adsorbed fluid forms an ordered structure close to a smoothed solid surface. This ordered structure is modelled as a collection of parallel molecular layers. Such a structure allows us to express the Helmholtz free energy of a molecular layer as the sum of the intrinsic Helmholtz free energy specific to that layer and the potential energy of interaction of that layer with all other layers and the solid surface. The intrinsic Helmholtz free energy of a molecular layer is a function (at given temperature) of its two-dimensional density and it can be readily obtained from bulk-phase properties, while the interlayer potential energy interaction is determined by using the 10-4 Lennard-Jones potential. The positions of all layers close to the graphite surface or in a slit pore are considered to correspond to the minimum of the potential energy of the system. This model has led to accurate predictions of nitrogen and argon adsorption on carbon black at their normal boiling points. In the case of adsorption in slit pores, local isotherms are determined from the minimization of the grand potential. The model provides a reasonable description of the 0-1 monolayer transition, phase transition and packing effect. The adsorption of nitrogen at 77.35 K and argon at 87.29 K on activated carbons is analyzed to illustrate the potential of this theory, and the derived pore-size distribution is compared favourably with that obtained by the Density Functional Theory (DFT). The model is less time-consuming than methods such as the DFT and Monte-Carlo simulation, and most importantly it can be readily extended to the adsorption of mixtures and capillary condensation phenomena.