Carbonation of alkaline paper mill waste to reduce CO2 greenhouse gas emissions into the atmosphere

International audienceThe global warming of Earth's near-surface, air and oceans in recent decades is a direct consequence of anthropogenic emission of greenhouse gases into the atmosphere such as CO2, CH4, N2O and CFCs. The CO2 emissions contribute approximately 60% to this climate change. This study investigates experimentally the aqueous carbonation mechanisms of an alkaline paper mill waste containing about 55 wt% portlandite (Ca(OH)2) as a possible mineralogical CO2 sequestration process. The overall carbonation reaction includes the following steps: (1) Ca release from portlandite dissolution, (2) CO2 dissolution in water and (3) CaCO3 precipitation. This CO2 sequestration mechanism was supported by geochemical modelling of final solutions using PHREEQC software, and observations by scanning electron microscope and X-ray diffraction of final reaction products. According to the experimental protocol, the system proposed would favour the total capture of approx. 218 kg of CO2 into stable calcite/ton of paper waste, independently of initial CO2 pressure. The final product from the carbonation process is a calcite (ca. 100 wt%)-water dispersion. Indeed, the total captured CO2 mineralized as calcite could be stored in degraded soils or even used for diverse industrial applications. This result demonstrates the possibility of using the alkaline liquid–solid waste for CO2 mitigation and reduction of greenhouse effect gases into the atmosphere

Mineral sequestration of CO2 by aqueous carbonation of coal combustion fly-ash

International audienceThe increasing CO2 concentration in the Earth's atmosphere, mainly caused by fossil fuel combustion, has led to concerns about global warming. A technology that could possibly contribute to reducing carbon dioxide emissions is the in-situ mineral sequestration (long term geological storage) or the ex-situ mineral sequestration (controlled industrial reactors) of CO2. In the present study, we propose to use coal combustion fly-ash, an industrial waste that contains about 4.1 wt.% of lime (CaO), to sequester carbon dioxide by aqueous carbonation. The carbonation reaction was carried out in two successive chemical reactions, first, the irreversible hydration of lime. CaO + H2O → Ca(OH)2 second, the spontaneous carbonation of calcium hydroxide suspension. Ca(OH)2 + CO2 → CaCO3 + H2O A significant CaO–CaCO3 chemical transformation (approximately 82% of carbonation efficiency) was estimated by pressure-mass balance after 2 h of reaction at 30 °C. In addition, the qualitative comparison of X-ray diffraction spectra for reactants and products revealed a complete CaO–CaCO3 conversion. The carbonation efficiency of CaO was independent on the initial pressure of CO2 (10, 20, 30 and 40 bar) and it was not significantly affected by reaction temperature (room temperature “20–25”, 30 and 60 °C) and by fly-ash dose (50, 100, 150 g). The kinetic data demonstrated that the initial rate of CO2 transfer was enhanced by carbonation process for our experiments. The precipitate calcium carbonate was characterized by isolated micrometric particles and micrometric agglomerates of calcite (SEM observations). Finally, the geochemical modelling using PHREEQC software indicated that the final solutions (i.e. after reaction) are supersaturated with respect to calcium carbonate (0.7 ≤ saturation index ≤ 1.1). This experimental study demonstrates that 1 ton of fly-ash could sequester up to 26 kg of CO2, i.e. 38.18 ton of fly-ash per ton of CO2 sequestered. This confirms the possibility to use this alkaline residue for CO2 mitigation

Arsenite sorption and co-precipitation with calcite

Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is limited by the amount of surface sites (ST), yields 6 sites nm-2 in good agreement with crystallographic data. Beyond this value, the amount of sorbed arsenic increases linearly with solution concentration, up to the saturation of arsenic with respect to the precipitation of CaHAsO3(s). The solid solutions formed in this concentration range were examined by X-ray and neutron diffraction. The doped calcite lattice parameters increase with arsenic content while c/a ratio remains constant. Our results made on bulk calcite on the atomic displacement of As atoms along [0001] direction extend those published by Cheng et al., (1999) on calcite surface. This study provides a molecular-level explanation for why As(III) is trapped by calcite in industrial treatments.Comment: 9 page

Synthesis of a Se0/Calcite Composite Using Hydrothermal Carbonation of Ca(OH)2 Coupled to a Complex Selenocystine Fragmentation

International audienceElemental selenium (Se0)/calcite composites were synthesized in a batch system by hydrothermal carbonation of calcium hydroxide under high CO2−Ar pressure (90 bar) and high temperature (90 °C) coupled to a complex selenocystine fragmentation. Under O2-poor conditions, the composite consisted predominantly of spherical, amorphous nanoparticles of elemental red selenium (<500 nm) deposited on the calcite matrix. Conversely, under O2-rich conditions, the composite consisted rod-shaped, well-crystallized microparticles of elemental gray selenium (<25 µm) dispersed in the calcite matrix. The carbonate matrix was constituted by nano- to microrhombohedral crystals (<2 µm) and micrometric agglomerates and/or aggregates (<5 µm). Our results present a new synthesis path to Se0/calcite composites, with spherical or rod-shaped Se0 morphology with high potential for medical (e.g., dietary supplement) or industrial (e.g., pigments) applications. Furthermore, this study may have implications in the field of biomineralization

Electron transfer at the mineral/water interface: Selenium reduction by ferrous iron sorbed on clay

International audienceThe mobility and availability of the toxic metalloid selenium in the environment is largely controlled by sorption and redox reactions, which may proceed at temporal scales similar to that of subsurface water movement under saturated or unsaturated conditions. Since such waters are often anaerobic and rich in Fe2+, we investigated the long-term (≤ 1 month) kinetics of selenite (Se(IV)O3 -) sorption to montmorillonite in the presence of Fe2+ under anoxic conditions. A synthetic montmorillonite was used to eliminate the influence of structural Fe. In the absence of aqueous Fe2+, selenite was sorbed as outer-sphere sorption complex, covering only part of the positive edge sites, as verified by a structure-based MUSIC model and Se K-edge XAS (X-ray absorption spectroscopy). When selenite was added to montmorillonite previously equilibrated with Fe2+ solution however, slow reduction of Se and formation of a solid phase was observed with Se K-edge XANES (x-ray absorption near-edge spectroscopy) and EXAFS (extended x-ray absorption finestructure) spectroscopy. Iterative transformation factor analysis of XANES and EXAFS spectra suggested that only one Se reaction product formed, which was identified as nano-particulate Se(0). Even after one month, only 75% of the initially sorbed Se(IV) was reduced to this solid species. Mössbauer spectrometry revealed that before and after addition and reduction of Se, 5% of total sorbed Fe occurred as Fe(III) species on edge sites of montmorillonite (≈ 2 mmol kg-1). The only change observed after addition of Se was the formation of a new Fe(II) species (15%) attributed to the formation of an outer-sphere Fe(II)-Se sorption complex. The combined Mössbauer and XAS results hence clearly suggest that the Se and Fe redox reactions are not directly coupled. Based on the results of a companion paper, we hypothesize that the electrons produced in the absence of Se by oxidation of sorbed Fe(II) are stored, for example by formation of surface H2 species, and are then 3 available for the later Se(IV) reduction. The slow reaction rate indicates a diffusion controlled process. Homogeneous precipitation of an iron selenite was thermodynamically predicted and experimentally observed only in the absence of clay. Interestingly, half of Fe was oxidized in this precipitate (Mössbauer). Since DFT calculations predicted the oxidation of Fe at the water-FeSe solid interface only and not in the bulk phase, the average particle size of this precipitate does not exceed 2 nm. A comparison with the Mössbauer and XAS spectra of the clay samples demonstrates that such homogenous precipitation can be excluded as a mechanism for the observed slow Se reduction, emphasizing the role of abiotic, heterogeneous precipitation and reduction for the removal of Se from subsurface waters

Decitabine impact on the endocytosis regulator RhoA, the folate carriers RFC1 and FOLR1, and the glucose transporter GLUT4 in human tumors.

BackgroundIn 31 solid tumor patients treated with the demethylating agent decitabine, we performed tumor biopsies before and after the first cycle of decitabine and used immunohistochemistry (IHC) to assess whether decitabine increased expression of various membrane transporters. Resistance to chemotherapy may arise due to promoter methylation/downregulation of expression of transporters required for drug uptake, and decitabine can reverse resistance in vitro. The endocytosis regulator RhoA, the folate carriers FOLR1 and RFC1, and the glucose transporter GLUT4 were assessed.ResultsPre-decitabine RhoA was higher in patients who had received their last therapy &gt;3&nbsp;months previously than in patients with more recent prior therapy (P = 0.02), and varied inversely with global DNA methylation as assessed by LINE1 methylation (r = -0.58, P = 0.006). Tumor RhoA scores increased with decitabine (P = 0.03), and RFC1 also increased in patients with pre-decitabine scores ≤150 (P = 0.004). Change in LINE1 methylation with decitabine did not correlate significantly with change in IHC scores for any transporter assessed. We also assessed methylation of the RFC1 gene (alias SLC19A1). SLC19A1 methylation correlated with tumor LINE1 methylation (r = 0.45, P = 0.02). There was a small (statistically insignificant) decrease in SLC19A1 methylation with decitabine, and there was a trend towards change in SLC19A1 methylation with decitabine correlating with change in LINE1 methylation (r = 0.47, P &lt;0.15). While SLC19A1 methylation did not correlate with RFC1 scores, there was a trend towards an inverse correlation between change in SLC19A1 methylation and change in RFC1 expression (r = -0.45, P = 0.19).ConclusionsIn conclusion, after decitabine administration, there was increased expression of some (but not other) transporters that may play a role in chemotherapy uptake. Larger patient numbers will be needed to define the extent to which this increased expression is associated with changes in DNA methylation

Studies on the Response of Tribolium castaneum (Herbst) (Coleoptera: Tenebrionidae) to Multicolour Light System

Tribolium castaneum (Herbst) (Coleoptera: Tenebrionidae) commonly known as rust red flour beetle was a universal pest of stored produce with an extensive feeding diversity. The management of T. castaneum in field conditions was through fumigation and spraying of suitable insecticides. Even though many plant products were found effective against pests in invitro conditions, they could not be mixed with the stored produce for fear of losing the table quality. Physical forces seemed to be good alternatives to chemical treatment as far as stored grain pests were concerned. The use of gamma and UV radiations, microwaves and ultrasonic sound waves against T. castaneum and other stored grain pests had been tried by many authors. The objectives of this study were to check the adult beetles and final instar grubs of T. castaneum to different colours of light and it showedpreference for clear tungsten (white) light, while they were averse to red coloured light. This trend was explicit even after the entrainment of beetles to red colour light for further generations. Based on these results it could be presumed that T. castaneum adults preferred to move away from red coloured light. By changing the colour of bright light to dark lighting in warehouses, it could be possible to manage T. castaneum in small measure. Total eradication of stored product pests like T. castaneum was at least possibility and the selection of a proper management system could help to solve the stored produce pest problem to a greater magnitude

Bose-Einstein source of intermittency in hadronic interactions

The multi-particle Bose-Einstein correlations are the source of ''intermittency'' in high energy hadronic collisions. The power-law like increase of factorial moments with decreasing bin size was obtained by complete event weighing technique with gaussian approximation of space-time particle emitting source shape. The value of source size parameter was found to be higher than the common one fitted with the help of the standard Handbury Brown-Twiss procedure.Comment: 12

Integral correlation measures for multiparticle physics

We report on a considerable improvement in the technique of measuring multiparticle correlations via integrals over correlation functions. A modification of measures used in the characterization of chaotic dynamical sytems permits fast and flexible calculation of factorial moments and cumulants as well as their differential versions. Higher order correlation integral measurements even of large multiplicity events such as encountered in heavy ion collisons are now feasible. The change from ``ordinary'' to ``factorial'' powers may have important consequences in other fields such as the study of galaxy correlations and Bose-Einstein interferometry.Comment: 23 pages, 6 tar-compressed uuencoded PostScript figures appended, preprint TPR-92-4

Multi-Jet Event Rates in Deep Inelastic Scattering and Determination of the Strong Coupling Constant

Jet event rates in deep inelastic ep scattering at HERA are investigated applying the modified JADE jet algorithm. The analysis uses data taken with the H1 detector in 1994 and 1995. The data are corrected for detector and hadronization effects and then compared with perturbative QCD predictions using next-to-leading order calculations. The strong coupling constant alpha_S(M_Z^2) is determined evaluating the jet event rates. Values of alpha_S(Q^2) are extracted in four different bins of the negative squared momentum transfer~\qq in the range from 40 GeV2 to 4000 GeV2. A combined fit of the renormalization group equation to these several alpha_S(Q^2) values results in alpha_S(M_Z^2) = 0.117+-0.003(stat)+0.009-0.013(syst)+0.006(jet algorithm).Comment: 17 pages, 4 figures, 3 tables, this version to appear in Eur. Phys. J.; it replaces first posted hep-ex/9807019 which had incorrect figure 4