Impact of Changes in Redox Conditions on Leaching of Some Elements from MSW Fly Ash

Abstract. Oxidation and reduction processes can influence extent of leaching of elements from solid waste. Three samples of municipal solid waste combustion fly ash were subjected to oxidizing and reducing conditions in order to evaluate leaching of elements in the Milli-Q water and fly ash (liquid to solid ratio, 100) mixtures. Although the oxidizing and reducing conditions were applied for 6 hours only, elements like Cs, Li, Mg, Sb, Tl and V leached more under oxidizing condition than under reducing condition in the case of all three ash samples. Cadmium, Pb and Zn leached more from all samples under reducing condition than under oxidizing condition. Leaching of other elements like Al, Ba, Cr, Cu, Ni and Rb was inconsistent with oxidizing or reducing conditions and varied from sample to sample, suggesting that factors other than redox may be more important in controlling leaching of these elements. Strong acid neutralization capacity of the fly ash samples let the pH vary within a narrow range, and thus severely limited the extent of leaching during the course of the experiment. Lead and Zn were the most sensitive while K and Na were the least sensitive to changes in redox conditions.     

Temperature and pH Dependence of Some Metals Leaching from Fly Ash of Municipal Solid Waste

Abstract. Municipal solid waste combustion leads to concentration of various metals in the solid residue (fly ash) remaining after combustion. These metals pose serious environmental hazard and require proper handling and monitoring in order to control their harmful effects. Leachability of some metals from fly ash was examined in fly ash and Milli-Q water mixture (liquid-to-solid ratio, 100) under various temperature and pH conditions in the laboratory. The leaching experiments conducted for 24 hours showed that pH was generally more important than temperature in controlling the amount of metals leached out of the fly ash. However, at a given pH, rise in temperature led to different degree of (usually one to two fold) enhanced or reduced leaching of metals. Owing to amphoteric nature of oxides of Al, Cr, Pb and Zn, these metals often yielded typical pattern of increase and decrease in their concentrations with change in pH. The extent of leaching of Cr and Pb in our experiments suggests that decrease of pH to acidic range in the case of Pb and to neutral to acidic range for Cr over a long period of storage of fly ash at solid waste dumping site may facilitate leaching of these metals from fly ash, leading to contamination of groundwater to the level that exceeds beyond the level permitted by the environmental laws.     

Modelling size effect on rock aggregates strength using a DEM bonded-cell model

Empirical evidence has shown that particle breakage affects the mechanical behaviour of granular materials. The source of this mechanism takes place at the particle scale, and the main consequence on the macromechanical behaviour is increasing compressibility. Due to the inverse correlation between particle size and particle crushing strength, coarse rockfill materials are particularly vulnerable to mechanical degradation due to particle breakage. However, such coarse materials do not fit in standard laboratory devices, and the alternative of large sample testing is usually unavailable or too expensive. Alternatively, recent works have proposed multi-scale approaches using the discrete element method (DEM) to carry out numerical testing of coarse crushable materials, although few studies have focused on size effects. This article presents the application of a DEM bonded-cell model to study particle size-strength correlation on angular rock aggregates. Each particle is modelled by a cluster of perfectly rigid polyhedral cells with Mohr–Coulomb contact law. Constant cell density within particles implies that the presence of potential fragmentation planes increases with size. Therefore, particle strength decreases with size. A comprehensive sensitivity analysis was carried out through 1477 particle crushing simulations in a given particle size. Based on published experimental data on calcareous rock aggregates, part of the simulations were used for calibration, and 97 additional simulations of a coarser size fraction were performed for validation. The results show a good agreement with the empirical data in terms of size effect and data scatter through Weibull statistics.

     

Ozone variation in the lower stratosphere and its mechanism

Seasonal variations of ozone are studied by taking into consideration both photochemical and dynamical processes. Assuming that the seasonal variations of total ozone amounts are linear combinations of photochemical equilibrium variations and those due to atmospheric motions, the observed variations of the total ozone amount seem reasonably to be explained.The concept mentioned above implies that the time scale of ozone might be rather short in the lower stratosphere. The order of the half restoration time was estimated to be 10 to 10² days in the lower stratosphere. Thus the estimated time scale of ozone must be somewhat longer than that of the temperature in the lower stratosphere, of which variation usually shows its maximum in the midwinter in middle latitudes, while that of ozone shows its maximum in the late winter or early spring. As the maximum values of both quantities would appear in the early summer without air motions, the similarity in the phase differences of temperature and ozone suggests the validity of the concept of this paper.     

Experimental study of the alteration process of labradorite in acid hydrothermal solutions

Labradorite was altered artificially by HC1 solution ranging from M = 1 to M = 0.003 at 245 and 230°C. The products of alteration were examined by X-ray diffraction, electron microscopy, electron diffraction, infrared spectroscopy and the electron microprobe and the solution was analyzed chemically.Amorphous silica only was formed in solutions with M_HCl = 1 and M_HCl = 0.3. In a solution with M_HCl = 0.2, amorphous silica was initially formed, later dissolved and replaced by kaolinite. A mixture of microcrystalline boehmite and amorphous aluminosilicate was formed, altering to kaolinite in solutions with M_HCl = 0.1 and 0.3. Small amounts of kaolinite were initially formed but the alteration soon stopped in solution with M_HCl = 0.003. Relationships between the alteration processes and pH of the solutions can be roughly explained by using solubility diagrams assuming the congruent dissolution of labradorite and precipitation of the products in partial equilibrium. However, these assumptions are not valid with strongly acid solutions.The rate of dissolution of labradorite is controlled not only by its surface area, but also by the diffusion of matter through the layer of alteration products.     

Otolith Microstructure Analysis Reveals Different Growth Histories of Japanese Sardine (Sardinops melanostictus) in the Oyashio Waters

After decades of low year classes,the stock of Japanese sardine(Sardinops melanostictus)has begun to recover since the mid-2000s.The hatch dates and otolith growth rates of age-0 juvenile sardine,which were collected in the subarctic Oyashio waters in autumn 2018,were determined from an otolith microstructure analysis.The sardines were hatched from late January to late April,while mostly in February and March.The otolith growth rate increased continuously up to 60 d after hatching and thereafter de-creased.The revealed growth rate in a crucial growth period is faster than that reported for juvenile sardines collected in the 1990s,which is coincided with the recent recovery trend of the sardine stock.Two groups with different hatch dates,growth histories,and migration routes were identified using unsupervised random forest clustering analysis.They were considered inshore and offshore migration individuals in accordance with recent researches.In the offshore group,a high proportion of sardine juveniles hatched late and grew faster in the Kuroshio-Oyashio transitional waters,a finding consistent with the hypothesis of growth-rate-dependent re-cruitment.This finding on the population composition and growth rate of juvenile sardine in the Oyashio waters can be a basis for an improved prediction of their survival and provides us with valuable information on the recruitment processes of this stock during the period of stock recovery.     

A study of rock alteration process based on kinetics of hydrothermal experiment

Experimental investigation was made on hydrothermal alteration of sericite in acid solution. It is found that the sericite is changed to pyrophyllite through kaolinite at 270° C and 260° C, and the alteration is considered to be a consecutive reaction involving two steps, from sericite to kaolinite and from kaolinite to pyrophyllite. On the other hand, pyrophyllite is not formed at 190° C and the sericite is altered to kaolinite. The rate of reaction in each step of this hydrothermal alteration is dependent on reaction temperature and chemical composition of the solution. From the results of the quantitative analyses of the experimental products, kinetic constants and related parameters were obtained.By using these numerical values, an alteration process can be followed in a given model. Computed results for some cases of an alteration of sericite in acid solution are presented. Geological phenomena such as rock alteration or weathering are thought to progress in a disequilibrium state and in an open system. An attempt described in this paper is a physicochemical approach to treat an alteration process accompanied with material transfer occurring in an open system from a kientic viewpoint.     

Isotope systematics of Li, Sr, Nd, and volatiles in Indian Ocean MORBs of the Rodrigues Triple Junction: Constraints on the origin of the DUPAL anomaly

The DUPAL anomaly, a radiogenic isotope anomaly discovered in the Indian Ocean mantle, has been interpreted as due to a large-scale mantle heterogeneity. To provide new constraints on the DUPAL origin, we analyzed isotope ratios of Li, Sr, and Nd in fresh N-MORB glasses recovered from the Rodrigues Triple Junction in the Indian Ocean, and from the North Atlantic. The Li isotopic compositions of the Indian Ocean DUPAL N-MORBs were comparable to those of the North Atlantic non-DUPAL N-MORBs. The source of the DUPAL signature in Indian Ocean MORBs and the E-MORB-type enriched mantle source have quite different Li isotopic compositions. The ¹⁴³Nd/¹⁴⁴Nd values of both sources are significantly lower than those of the North Atlantic N-MORBs. The δ⁷Li values of most oceanic island basalts with similar low ¹⁴³Nd/¹⁴⁴Nd signatures are also higher than those of the North Atlantic N-MORBs, except for several Koolau lavas. The Li isotope results support the recent proposal that significant amounts of recycled lower continental crust might produce the radiogenic isotope signatures of the Indian Ocean DUPAL source.     

Lithium and strontium isotopic systematics in playas in Nevada,USA: constraints on the origin of lithium

Lithium-rich brine in playas is a major raw material for lithium production. Recently, lithium isotopic ratios (δ⁷Li) have been identified as a tool for investigating water–rock interactions. Thus, to constrain the origin of lithium in playas by the use of its isotopes, we conducted leaching experiments on various lacustrine sediment and evaporite deposit samples collected from playas in Nevada, USA. We determined lithium and strontium isotopic ratios and contents and trace element contents of the leachate, estimated the initial δ⁷Li values in the water flowing into the playas, and examined the origin of lithium in playas by comparison with δ⁷Li values of the possible sources. In samples from the playas, δ⁷Li values show some variation, reflecting differences both in isotopic fractionation during mineral formation and in initial δ⁷Li value in water flowing into each playa. However, all δ⁷Li values in this study are much lower than those in river water and groundwater samples from around the world, but they are close to those of volcanic rocks. Considering the temperature dependence of lithium isotopic fractionation between solid and fluid, these results indicate that the lithium concentrated in playas in Nevada was supplied mainly through high-temperature water–rock interaction associated with local hydrothermal activity and not directly by low-temperature weathering of surface materials. This study, which is the first to report lithium isotopic compositions in playas, demonstrates that δ⁷Li may be a useful tracer for determining the origin of lithium and evaluating its accumulation processes in playas.