Guest Comments: Human Activities and the Integrity of Lake Ecosystems

Water, Air, &; Soil Pollution: Focus -     

On equilibration of pore water in column leaching tests

Column leaching tests are closer to natural conditions than batch shaking tests and in the last years have become more popular for assessing the release potential of pollutants from a variety of solids such as contaminated soils, waste, recycling and construction materials. Uncertainties still exist regarding equilibration of the percolating water with the solids, that might potentially lead to underestimation of contaminant concentrations in the effluent. The intention of this paper is to show that equilibration of pore water in a finite bath is fundamentally different from release of a certain fraction of the pollutant from a sample and that equilibrium is reached much faster at low liquid-to-solid ratios typical for column experiments (<0.25) than in batch tests with much higher liquid-to-solid ratios (e.g. 2–10). Two mass transfer mechanisms are elucidated: First-order type release (film diffusion) and intraparticle diffusion. For the latter, mass transfer slows down with time and sooner or later non-equilibrium conditions are observed at the column outlet after percolation has been started. Time scales of equilibrium leaching can be estimated based on a comparison of column length with the length of the mass transfer zone, which is equivalent to a Damköhler number approach. Mass transfer and diffusion coefficients used in this study apply to mass transfer mechanisms limited by diffusion in water, which is typical for release of organic compounds but also for dissolution of soluble minerals such as calcite, gypsum or similar. As a conclusion based on these theoretical considerations column tests (a) equilibrate much faster than batch leaching tests and (b) the equilibrium concentrations are maintained in the column effluent even for slow intraparticle diffusion limited desorption for extended periods of time (>days). Since for equilibration the specific surface area is crucial, the harmonic mean of the grain size is relevant (small grain sizes result in high concentrations even after short pre-equilibration of a column). The absolute time scales calculated with linear sorption and aqueous diffusion aim at organic compounds and are not valid for sparingly soluble mineral phases (e.g. metal oxides and silicates). However, the general findings on how different liquid-to-solid ratios and specific surface area influence equilibration time scales also apply to other mass transfer mechanisms.     

Evaluating biotoxicity variations of landfill leachate as penetrating through the soil column

Recent studies of leachate-induced ecotoxicity have focused on crude samples, while little attention has been given to changes in biotoxicity resulting from the environmental behavior of landfill leachate. Therefore, we set up a soil column to simulate the underground penetration of leachate into the soil layer, define the rules of migration and transformation of leachate pollutants, and determine the variation in toxicity of landfill leachate during penetration. The results demonstrated that: (1) landfill leachate inhibited the growth and chlorophyll levels, elevated the levels of lipid peroxidation and protein oxidation, and stimulated the antioxidant enzyme activities of barley seedlings. The effects generally displayed a peak value at 12–24 cm, slowly declined at 36–48 cm, and then rapidly decreased with penetrating distance in the column. (2) Statistical correlation analysis of the properties of leachate and the observed biotoxic effects revealed that COD, conductivity and heavy metals (esp. Ni, Mn, Cd) were positively correlated with variations in biotoxicity. (3) The microbial activity of outflowing leachate sampled from the 48 cm port was significantly higher than the activity from succedent ports, and the types of contaminants increased in the leachate outflowing from the same port, implying that microbial behaviors near the 48 cm port could be used to partially evaluate variations in the composition and biotoxicity of landfill leachate. Taken together, the above results illustrate the polluting characteristics of landfill leachate when penetrating a soil column and provide guidance for pollution control and risk assessment of landfill leachate.     

Leaching from MSWI bottom ash: evaluation of non-equilibrium in column percolation experiments

Impacts of non-equilibrium on results of percolation experiments on municipal solid waste incineration (MSWI) bottom ash were investigated. Three parallel column experiments were performed: two columns with undisturbed percolation and one column with two sets of 1-month-long flow interruptions applied at liquid-to-solid (L/S) ratios of L/S 2L/kg and 12L/kg, respectively. Concentrations of Na, K, Cl(-), Ca, Si, SO(4)(2-), Al, Cu, Ni, Mo, Ba, Pb, Zn, and dissolved organic carbon (DOC) were monitored throughout the entire leaching period; geochemical modeling was used to identify non-equilibrium-induced changes in the solubility control. Despite both physical and chemical non-equilibrium, the columns were found to provide adequate information for readily soluble compounds (i.e., Na, Cl(-), and K) and solubility-controlled elements (i.e., Ca, SO(4)(2-), Ba, Si, Al, Zn, and Pb). The leaching of Cu and Ni was shown to depend strongly on DOC leaching, which was likely affected by physical non-equilibrium during flow interruptions. Consequently, the leaching of Cu and Ni in the undisturbed columns was shown to be by about one order of magnitude lower compared with the interrupted column. The results indicate that the leaching of DOC-related metals in laboratory column experiments may be considerably underestimated compared with full-scale scenarios in which the impacts from non-equilibrium may be significantly lower. The leaching of Mo (or MoO(4)(2-)) may be controlled solely by its availability in the mobile zone, which in turn appeared to be controlled by diffusion from the stagnant zone; no Mo controlling minerals were predicted by the geochemical modeling.     

Removal of unburned carbon from municipal solid waste fly ash by column flotation

Unburned carbon (UC) is the major source of organic contaminants in municipal solid waste (MSW) fly ash. So most organic contaminants can be removed by the removal of the UC from the MSW fly ash. In this paper, we first used a technique of column flotation to remove UC from MSW fly ash. The influences of column flotation parameters on the recovery efficiency of UC were systematically studied. It was found that the UC recovery efficiency was greatly influenced by the gas flow rate, pH value, collector kerosene's concentration and the types of fly ash. By optimizing the above parameters, we have successfully removed 61.2% of the UC from MSW fly ash having 5.24% UC content. The removal mechanism was well accounted for the kinetic theory of column flotation and surface-chemistry theory. The results indicate that the column flotation technique is effective in removing the UC from MSW fly ash, and show that there is a strong possibility for practical application of this technique in removing the organic contaminants from MSW fly ash.     

Batch and column tests of metal mobilization in soil impacted by landfill leachate

The percolation of landfill leachate, even in the absence of a high concentration of specific pollutant, may induce a strong modification of soil chemical and physical characteristics, due to the alteration of the natural equilibrium between the aqueous phase and the soil matrix. As a result, a huge amount of cations can be solubilized, thus inducing groundwater pollution.In this work batch and column experiments of metal mobilization from a soil sampled down gradient of a municipal waste landfill in Northern Italy are presented. The experiments were initially performed in batch scale on soil slurries at different pH and Eh. Distilled water was used first and then a groundwater sampled down-gradient in the same site. Subsequently, to better simulate the aquifer conditions, 50 d column tests were performed on 15 kg of saturated soil. The concentrations of Fe, Mn, and Ni were evaluated when these selected environmental parameters were altered. Results indicated a greater release when acidic conditions were achieved, a positive effect in this case of the addition of an oxidant and a great Mn mobilization when negative redox potentials were established.     

Comparison of the release of constituents from granular materials under batch and column testing

Column leaching testing can be considered a better basis for assessing field impact data than any other available batch test method and thus provides a fundamental basis from which to estimate constituent release under a variety of field conditions. However, column testing is time-intensive compared to the more simplified batch testing, and may not always be a viable option when making decisions for material reuse. Batch tests are used most frequently as a simple tool for compliance or quality control reasons. Therefore, it is important to compare the release that occurs under batch and column testing, and establish conservative interpretation protocols for extrapolation from batch data when column data are not available. Five different materials (concrete, construction debris, aluminum recycling residue, coal fly ash and bottom ash) were evaluated via batch and column testing, including different column flow regimes (continuously saturated and intermittent unsaturated flow). Constituent release data from batch and column tests were compared. Results showed no significant difference between the column flow regimes when constituent release data from batch and column tests were compared. In most cases batch and column testing agreed when presented in the form of cumulative release. For arsenic in carbonated materials, however, batch testing underestimates the column constituent release for most LS ratios and also on a cumulative basis. For cases when As is a constituent of concern, column testing may be required.     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

Performance characteristics and modeling of carbon dioxide absorption by amines in a packed column

Absorption of carbon dioxide by amines in a packed column was experimentally investigated. The amines employed in the present study were the primary mono-ethanolamine (MEA) and tertiary N-methyldiethanolamine (MDEA), two very popular amines widely used in the industries for gas purification. The CO₂ absorption characteristics by these two amines were experimentally examined under various operating conditions. A theoretical model was developed for describing the CO₂ absorption behavior. Test data has revealed that the model predictions and the observed CO₂ absorption breakthrough curves agree very well, validating the proposed model. Preliminary regeneration tests of exhausted amine solution were also conducted. The results indicated that the tertiary amine is easier to regenerate with less loss of absorption capacity than the primary one.     

Evaluation of carbonization as a thermal pretreatment method for landfilling by column leaching tests

To evaluate carbonization as a thermal pretreatment method for landfilling, the releasing characteristics of organic and inorganic constituents from carbonization residue derived from shredded residue of bulky waste was investigated by means of batch and column leaching tests. Shredded residue of bulky waste itself and its incineration ash were tested together to compare pretreatment methods. In batch leaching tests at a liquid/solid ratio of 10, the release of organic carbon from carbonization residue was at a remarkably low level. Besides, carbonization contributed to immobilize heavy metals such as chromium, cadmium, and lead within its residue. In column tests, the discharges of organic constituents were lowest from carbonization residue under aerobic conditions due to microbial activity. The leaching of Cd, Cr, Pb, and Cu from carbonization residue was suppressed under anaerobic conditions; however, this suppression effect tended to be weaker under aerobic conditions. From the results showing that the total releasing amounts of organic and inorganic constituents from carbonization residue are so low as to be comparable to that of incineration ash, carbonization can be considered as one of the thermal pretreatment methods of organic wastes.     

Investigation of naphtalene sulfonate compounds sorption in a soil artificially contaminated using batch and column assays

In the present work desorption tests of an artificially contaminated soil by naphatelene sulphonated compounds have been carried out by soil washing realised by water at different pH: Naphtalene-1,5-disulfonic acid (1-5 NDS), 2-naphthol-6,8 disulphonic acid (G-acid) and sodium beta-naphtalene-sulphonate (beta-salt) have been selected as more representative organic compounds present in the ex industrial site of ACNA (Cengio, SV, Italy) in which very serious contamination levels of several pollutants are present both in the soils and surface waters. Equilibrium batch tests have been carried out in order to find the best operative condition in column washing tests. The obtained results can be considered very preliminary but useful to arrange a next experimental work that will be realised on real contaminated soils.     

Effect of contact time on the release of contaminants from granular waste materials during column leaching experiments

When reusing or disposing of contaminated granular waste materials there is a need to evaluate how the contaminants will interact on the pathway soil–groundwater and the effect this interaction will have on the surrounding environment. While column testing can provide a closer approximation to field percolation conditions than batch testing, there is still a need to develop column testing procedures that consider the requirements of practical testing time frames. This study evaluates the effect of different column contact times (2.5, 5, and 16 h) on the release of inorganic constituents from bottom ash and demolition waste, two commonly reused granular materials. Leaching data for representative constituents of concern, such as copper, chromium, sulfate and chloride, as well as pH and electrical conductivity was compared for all different contact times studied.Results for the materials investigated in this study showed that variations in contact time have no significant effect on the release of the selected constituents and leaching parameters at low liquid to solid ratios. However, after a liquid to solid ratio of 1 L/kg, the effect is more noticeable, and higher contact times show lower pH values as well as a reduction in the release of constituents of concern from bottom ash. In the case of demolition waste, the variation of contact time did not have a strong effect on the leaching behavior.     

用四-(对氨基苯基)-卟啉柱前衍生的高效液相色谱法测定重金属

研究了用固相萃取富集、快速分离柱高效液相色谱法测定环境水样中镍、锡、铅、镉、汞5种重金属的方法。环境水样中的镍、锡、铅、镉、汞用四-(对氨基苯基)-卟啉(T4APP)柱前衍生,然后用ZORBAX RP18固相萃取小柱萃取富集镍、锡、铅、镉、汞的T4APP络合物,经富集后的络合物用甲醇-丙酮(体积比95∶5)为流动相,ZORBAX Stab le Bound(4.6 mm×50 mm,1.8μm)快速分离柱为固定相分离,用二极管矩阵检测器检测。镍、锡、铅、镉、汞的检测限分别为4,5,4,3,3 ng/L,分离5种重金属元素络合物的时间只需2.0 m in,相对标准偏差为2.2%~4.1%,加标回收率为88%~104%。用该法测定环境水样中的痕量镍、锡、铅、镉、汞,结果令人满意。     

Leaching behaviour of elements and evaluation of pre-treatment methods for municipal solid waste incinerator residues in column leaching tests.

Two new pre-treatment methods (water-washing/carbonation and carbonation/phosphate stabilization) of municipal solid waste (MSW) incinerator residues were evaluated by column leaching tests under aerobic conditions and anaerobic conditions (which were changed to aerobic conditions after 10 months). A mixture of bottom ash and fly ash (5:1 ratio) was pre-treated using each method. Shredded incombustible residues (SIR) were added to each ash preparation in proportions similar to the ratios present in landfills. For comparison, landfill wastes typical of Japan, namely, a mixture of bottom ash, chelating-pre-treated fly ash, and SIR, were also examined. Leachate samples were collected periodically and analysed over a 15-month period. When compared with chelating pretreatment, both water-washing/carbonation and carbonation/ phosphate stabilization reduced the leaching of Pb, Al, and Cu by about one to two orders of magnitude. Moreover, the initial concentrations of Ca and Pb in leachates from column of water-washing/carbonation were 56-57% and 84-96% less than those from the column of carbonation/phosphate stabilization. Therefore, water-washing/carbonation was considered to be a promising approach to obtain early waste stabilization and to reduce the release of heavy metals to near-negligible levels. The leaching behaviour of elements was also discussed.     

Flotation kinetics of aluminum powders derived from waste crystalline silicon solar cells and its comparison between batch,continuous and column flotation practices

Journal of Material Cycles and Waste Management - In this study, floatability rate of aluminum (Al) powders was analyzed for the purpose of separating valuable resources from residual materials in...