Behavior of metals in ash melting and gasification-melting of municipal solid waste (MSW)

In this study, metal behavior in ash-melting and municipal solid waste (MSW) gasification-melting facilities were investigated. Eight ash-melting and three MSW gasification-melting facilities with a variety of melting processes and feedstocks were selected. From each facility, melting furnace fly ash (MFA) and molten slag were sampled, and feedstock of the ash-melting processes was also taken. For the ash melting process, the generation rate of MFA was well correlated with the ratio of incineration fly ash (IFA) in feedstock, and this was because MFA was formed mostly by mass transfer from IFA and a limited amount from bottom ash (BA). Distribution ratios of metal elements to MFA were generally determined by volatility of the metal element, but chlorine content in feedstock had a significant effect on Cu and a marginal effect on Pb. Distribution ratio of Zn to MFA was influenced by the oxidizing atmosphere in the furnace. High MFA generation and distribution ratio of non-volatile metals to MFA in gasification-melting facilities was probably caused by carry-over of fine particles to the air pollution control system due to large gas volume. Finally, dilution effect was shown to have a significant effect on metal concentration in MFA.     

Leaching characteristics of rare metal elements and chlorine in fly ash from ash melting plants for metal recovery

In terms of resource recovery and environmental impact, melting furnace fly ash (MFA) is attracting much attention in Japan due to its high metal content. The study aims to obtain fundamental information on using a water extraction method not only to concentrate valuable rare metals but also to remove undesirable substances such as chlorine for their recovery from MFA. The composition and leaching characteristics of MFA was investigated. The results revealed that the metal content in MFA is nearly equal to raw ore quality. The content of Ag, In, Pd, Pb, and Zn is, in fact, higher than the content of raw ore. As for leaching behavior, Ag, Bi, In, Ga, Ge, Sb, Sn, and Te showed the lowest release at a neutral pH range. Pd was leached constantly regardless of pH, but its concentration was quite low. On the other hand, most of the Tl was easily leached, revealing that water extraction is not appropriate for Tl recovery from MFA. Major elements Cl, Ca, Na, and K, occupying about 70% of MFA, were mostly leached regardless of pH. Base metal elements Cu, Pb, and Zn showed minimum solubility at a neutral pH. The leaching ratio of target rare metal elements and base metal elements suggests that the optimal pH for water extraction is 8-10, at which the leaching concentration is minimized. The water extraction process removed most of the Cl, Ca, Na, and K, and the concentration of rare metals and base metals increased by four or five times.     

Ammoniacal leaching and recovery of copper from alloyed low-grade e-waste

The paper concerns a hydrometallurgical method for selective recovery of copper from low-grade electric and electronic wastes. The following consecutive stages were proposed: smelting of the scraps to produce Cu–Zn–Ag alloy, leaching of the alloy in ammoniacal solution, and selective copper electrowinning. Cu–Zn–Ag alloy was a polymetallic and five-phase system. It was leached in chloride, carbonate, sulfate and thiosulfate solutions. This resulted in the separation of the metals, wherein metallic tin and silver as well as lead salts remained in the slimes, while copper and zinc were transferred to the electrolyte. Copper was selectively recovered from the ammoniacal solutions by the electrolysis, leaving zinc ions in the electrolyte. The best conditions of the alloy treatment were obtained in the ammonia–carbonate system, where the final product was copper of high purity (99.9 %) at the current efficiency of 60 %. Thiosulfate solution was not applicable for the leaching of the copper alloy due to secondary reactions of the formation of copper(I) thiosulfate complexes and precipitation of copper(I) sulfide, both inhibiting dissolution of the metallic material.     

An investigation on the potential of metal recovery from the municipal waste incinerator in Taiwan

This study aimed to identify distribution of metals and to estimate the amount of these metals that can be potentially recovered from incineration residues. First, the partitioning behavior of Cr, Cu, Fe, Cd, Al, Zn, and Pb in bottom ash and fly ash was investigated in one large municipal waste incinerator in Taiwan. In addition, the material flow analysis (MFA) method was used to estimate the material flux of metals within incinerator plant, and to calculate the amount of metal recovery. According to the findings of this study, six metals (Fe, Al, Cu, Zn, Cr, and Pb) concentrated in bottom ash mostly, while Cd existed primarily in fly ash. The weight percentages of Fe (4.49%), Al (5.24%), Cu (1.29%), Zn (2.21%), and Pb (0.58%) in incinerator ash are high, and even higher than the compositions of natural minerals. Finally, the amount of Cr, Cu, Fe, Cd, Al, Zn and Pb that can be potentially recovered from incineration residues will reach 2.69 x 10(2), 1.46 x 10(4), 4.91 x 10(4), 6.92 x 10(1), 5.10 x 10(4), 1.85 x 10(4) and 4.66 x 10(3) ton/yr, respectively.     

Recovery of metals from waste printed circuit boards by supercritical water pre-treatment combined with acid leaching process

Waste printed circuit boards (PCBs) contain a large number of metals such as Cu, Sn, Pb, Cd, Cr, Zn, and Mn. In this work, an efficient and environmentally friendly process for metals recovery from waste PCBs by supercritical water (SCW) pre-treatment combined with acid leaching was developed. In the proposed process, waste PCBs were pre-treated by SCW, then the separated solid phase product with concentrated metals was subjected to an acid leaching process for metals recovery. The effect of SCW pre-treatment on the recovery of different metals from waste PCBs was investigated. Two methods of SCW pre-treatment were studied: supercritical water oxidation (SCWO) and supercritical water depolymerization (SCWD). Experimental results indicated that SCWO and SCWD pre-treatment had significant effect on the recovery of different metals. SCWO pre-treatment was highly efficient for enhancing the recovery of Cu and Pb, and the recovery efficiency increased significantly with increasing pre-treatment temperature. The recovery efficiency of Cu and Pb for SCWO pre-treatment at 420 °C was 99.8% and 80%, respectively, whereas most of the Sn and Cr were immobilized in the residue. The recovery of all studied metals was enhanced by SCWD pre-treatment and increased along with pre-treatment temperature. Up to 90% of Sn, Zn, Cr, Cd, and Mn could be recovered for SCWD pre-treatment at 440 °C.     

Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes

Used batteries contain numerous metals in high concentrations and if not disposed of with proper care, they can negatively affect our environment. These metals represent 83% of all spent batteries and therefore it is important to recover metals such as Zn and Mn, and reuse them for the production of new batteries. The recovery of Zn and Mn from used batteries, in particular from Zn–C and alkaline ones has been researched using hydrometallurgical methods. After comminution and classification of elemental components, the electrode paste resulting from these processes was treated by chemical leaching. Prior to the leaching process the electrode paste has been subjected to two washing steps, in order to remove the potassium, which is an inconvenient element in this type of processes. To simultaneously extract Zn and Mn from this paste, the leaching method in alkaline medium (NaOH solution) and acid medium (sulphuric acid solution) was used. Also, to determine the efficiency of extraction of Zn and Mn from used batteries, the following variables were studied: reagents concentration, S/L ratio, temperature, time. The best results for extraction yield of Zn and Mn were obtained under acid leaching conditions (2 M H₂SO₄, 1 h, 80 °C).     

Recovery of valuable metals from electronic and galvanic industrial wastes by leaching and electrowinning

In the present paper, a study on laboratory scale to perform a treatment for valuable metals recovery from electronic and galvanic industrial wastes, is reported. The characterisation of the waste, performed by XRD, SEM, EDX and chemical analysis, showed a high metals content in the sludge, such as Cu, Ni, Mn, Pb, Sn, W. A leaching process, coupled by electrowinning, is then proposed in order to reduce the volume of the waste material and to recover selectively valuable metals, such as Cu and Ni. During the leaching step, carried out by using H(2)SO(4), several factors were investigated (acid concentration, temperature and time of treatment). The leached liquor has been successfully treated with an electrowinning process, to recover copper and nickel. The copper and nickel depositions, were performed in acid and alkaline conditions, respectively. The Faraday yield was of about 95%. The energy consumption was 2.13 and 4.43 kWh per kg of copper and nickel recovered, respectively. At the end of the process, about 94-99% of the initial content of Cu and Ni was recovered at the cathode. The experimental results obtained, showed the technical feasibility of the process.     

Wet extraction of heavy metals and chloride from MSWI and straw combustion fly ashes

Fly ash residues from combustion often do not meet the criteria neither for reuse as construction materials nor landfilling as non-hazardous waste, mainly because of the high concentration of heavy metals and chlorides. This work aimed to technically evaluate an innovative wet treatment process for the extraction of chloride (Cl^?), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) from fly ashes from a municipal solid waste incineration (MSWI) plant and from a straw combustion (SC) facility. Factors investigated were liquid/solid (L/S) ratio, full carbonation (CO₂ treatment), influence of pH and leaching time, using a two-level full factorial design. The most significant factor for all responses was low pH, followed by L/S ratio. Multiple linear regression models describing the variation in extraction data had R² values ranging from 58% to 98%. An optimization of the element extraction models was performed and a set of treatment conditions is suggested.     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液,考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr,Zn,Cu,Pb,Ni,As,Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中,醋酸缓冲溶液法的重金属浸出种类最多,且浸出量最大;Cd和Cr对环境具有较高的潜在危害性,Cu次之,Zn,Pb,Ni,As主要以残渣态形式存在,对环境的直接危害性较低。     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.     

Immobilization of lead and zinc in scrubber residues from MSW combustion using soluble phosphates

The immobilization of MSWI-scrubber residues with soluble PO4(3-) was studied and compared to the immobilization using cement. The DIN 38414-S4 leaching protocol and pH dependent leaching were used to evaluate the leaching of Pb and Zn. Four different scrubber residues from MSW combustion (Pb concentration: 2.8-4.8 mg/g; Zn concentration: 3.0-12.3 mg/g) were mixed with water and cement or Na2HPO4 as source of soluble PO4(3-) at dosages of at least 0, 0.1, 0.2, 0.3 and 0.4 g per g residue. With cement as well as with PO4(3-) a reduction in Pb and Zn leaching was observed. With 0.4 g cement per g residue, the Pb leaching was reduced by a factor ranging from 70 to 100, but still exceeded the Pb landfill limit of 2 mg/l. With PO4(3-) the Pb leaching was reduced with a factor of 100-300 to below 2 mg/l. The Zn landfill limit (10 mg/l) was only exceeded by one untreated residue. Adding 0.2 g cement or 0.1 g PO4(3-) per g of that residue was enough to reduce leaching below 10 mg/l. However, when 0.6 g Na2HPO4 per g residue was added to a lime based scrubber residue, an increase in Zn leaching up to 12.5 mg/l was observed due to an increase in pH of up to 13.0. When using NaH2PO4 and H3PO4 no such increase in Zn leaching was observed. pH dependent leaching performed on one of the four residues showed that in the pH range of 2.5-6, Pb leaching was 100-50 times lower with Na2HPO4 treatment than with cement. In the pH range from 7-11, almost equal results were obtained for cement treated and Na2HPO4 treated residue. Above a pH of 12, Pb leaching was three times lower for the PO(4)(3-)-treated residue than for the cement treated residue. With soluble PO4(3-), Pb leaching below 2 mg/l could be attained at a dosage of 0.27 g PO4(3-)/g residue. With cement, Pb leaching was never below 2 mg/l.     

铅冶炼烟尘的物性分析及浸出性研究

采用XRF、XRD、激光粒度分析、DTA-TG、FTIR以及SEM-EDS等技术,对某铅冶炼厂烟尘（简称烟尘）进行了物性分析,并采用稀硫酸对烟尘进行了浸出性研究。分析结果表明：烟尘所含主要元素为Pb,Zn,Cd,Cl,S,As;烟尘是氧化物、硫酸盐、硅酸盐、硫化物和砷化物等物质的混合物,主要物相为ZnO,PbO,PbSO₄,CdO,CdS;烟尘颗粒大小不一,形状各异,多呈相互黏结或包裹状。实验结果表明：在ρ（硫酸）=120 g/L、浸出时间30 min、液固比（稀硫酸体积（mL）与烟尘质量（g）之比）20∶1、浸出温度60 ℃的条件下,Pb,Zn,Cd,As,Cl的浸出率分别达到0.16%,98.95%,49.36%,89.12%,99.31%。     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.     

Petrographic and spectroscopic characterization of phosphate-stabilized mine tailings from Leadville,Colorado

The use of soluble PO4(3-) and lime as a heavy metal chemical stabilization agent was evaluated for mine tailings from Leadville, Colorado. The tailings are from piles associated with the Wolftone and Maid of Erin mines; ore material that was originally mined around 1900, reprocessed in the 1940s, and now requires stabilization. The dominant minerals in the tailings are galena (PbS), cerrusite (PbCO3), pyromorphite (Pb5(PO4)3Cl), plumbojarosite (Pb0.5Fe3(SO4)2(OH)6), and chalcophanites ((Pb,Fe,Zn,Mn)Mn2O5 x 2H2O). The tailings were treated with soluble PO4(3-) and lime to convert soluble heavy metals (principally Pb, Zn, Cu, Cd) into insoluble metal phosphate precipitates. The treatment process caused bulk mineralogical transformations as well as the formation of a reaction rind around the particles dominated by Ca and P. Within the mineral grains, Fe-Pb phosphosulfates, Fe-Pb sulfates (plumbojarosite), and galena convert to Fe-Ca-Pb hydroxides. The Mn-Pb hydroxides and Mn-(+/-Fe)-Pb hydroxides (chalcophanites) undergo chemical alteration throughout the grains during treatment. Bulk and surface spectroscopies showed that the insoluble reaction products in the rind are tertiary metal phosphate (e.g. (Cu,Ca2)(PO4)2) and apatite (e.g. Pb5(PO4)3Cl) family minerals. pH-dependent leaching (pH 4,6,8) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 150 for many metals; particularly Pb2+, Zn2+, Cd2+, and Cu2+. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca2+, PO4(3-) Pb2+, Zn2+, Cd2+, and Cu2+ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids.     

Leaching behavior of heavy metals from municipal solid waste incineration bottom ash and its geochemical modeling

With the increase in the number of municipal solid waste incineration (MSWI) plants constructed in China recently, great attention has been paid to the heavy metal leaching toxicity of MSWI residues. In this study, the effects of various parameters, including extractant, leaching time, liquid-to-solid ratio, leachate pH, and heavy metal content, on the release properties of Cd, Cr, Cu, Ni, Pb, and Zn from MSWI bottom ash were investigated. Partial least-squares analysis was employed to highlight the interrelationships between the factors and response variables. Both experimental research and geochemical modeling using Visual MINTEQ software were conducted to study the pH-dependent leaching behavior of these metals in fresh and weathered bottom ash, considering precipitation/dissolution and surface complexation reactions (adsorption by hydrous ferric oxide and amorphous aluminum oxide/hydroxide). The results showed that leachate pH was the predominant factor influencing heavy metal leachability. The leaching of Cu, Pb, and Zn was mainly controlled by precipitation/dissolution reactions, whereas surface complexation had some effect on the leaching of Cr, Cd, and Ni for certain pH ranges. The modeling results aggreed well with the experimental results. Part of this work was presented at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

Water extraction with CO2 bubbling as pretreatment of melting-furnace fly ash for metal recovery

In Japan, melting-furnace fly ash (MFA) generated from ash melting and gasification/melting plants is considered an “urban mine” due to its high metal content. This study aimed to develop a novel approach to pretreating MFA for metal recovery. Water extraction with CO₂ bubbling was investigated because MFA mainly consists of water-soluble salts containing elements such as Cl, Ca, Na, and K. Instead of acid addition, CO₂ bubbling was applied to maintain the optimal pH for minimizing the release of target metal elements and maximizing the removal of undesirable elements during water extraction. The results revealed that CO₂ bubbling effectively decreased the release of Pb, Zn, and Cd into the treatment water. This was mainly due to coprecipitation with CaCO₃, which was primarily formed by the reaction of Ca²⁺ from the MFA with CO₃ ²⁻ from the CO₂ gas. The bubbling process also helped accelerate the removal of Cl from MFA. Furthermore, the study showed that it is possible to lower the water-to-solid ratio to 5 with only a slight reduction in water extraction effect. Finally, approximately four times the concentration of target metals (rare metals and Cu, Pb, and Zn) was achieved by removing 90% of Cl, 70%–90% of Na and K, and 30%–40% of Ca through water extraction with CO₂ bubbling, resulting in a concentration of target metals that was nearly equal to that of ore.     

Effects of chemical composition of fly ash on efficiency of metal separation in ash-melting of municipal solid waste

In the process of metal separation by ash-melting, Fe and Cu in the incineration residue remain in the melting furnace as molten metal, whereas Pb and Zn in the residue are volatilized. This study investigated the effects of the chemical composition of incineration fly ash on the metal-separation efficiency of the ash-melting process. Incineration fly ash with different chemical compositions was melted with bottom ash in a lab-scale reactor, and the efficiency with which Pb and Zn were volatilized preventing the volatilization of Fe and Cu was evaluated. In addition, the behavior of these metals was simulated by thermodynamic equilibrium calculations. Depending on the exhaust gas treatment system used in the incinerator, the relationships among Na, K, and Cl concentrations in the incineration fly ash differed, which affected the efficiency of the metal separation. The amounts of Fe and Cu volatilized decreased by the decrease in the molar ratio of Cl to Na and K in the ash, promoting metal separation. The thermodynamic simulation predicted that the chlorination volatilization of Fe and Cu was prevented by the decrease in the molar ratio, as mentioned before. By melting incineration fly ash with the low molar ratio in a non-oxidative atmosphere, most of the Pb and Zn in the ash were volatilized leaving behind Fe and Cu.     

氯化铵浸取法回收盐泥中的镁

以盐泥为原料,采用氯化铵浸取回收盐泥中的Mg²⁺,以浸取液和回收的氨反应制取氢氧化镁产品。考察了盐泥浆液固含量、浸取时间、物料比（氯化铵与盐泥中氢氧化镁的摩尔比）等工艺条件对Mg²⁺浸取率的影响,并以比表面积为考察指标进行正交实验,确定氢氧化镁的最佳制备条件。实验结果表明：在盐泥浆液固含量为248 g/L、浸取时间为100 min、物料比为2.3的条件下,Mg²⁺浸取率为75.0%;在n（MgCl₂）:n（NH₄Cl）=0.5、氨水浓度3 mol/L、氨水滴加速率 0.8 mL/min、反应温度 90 ℃的最佳条件下,制备的氢氧化镁的比表面积为17.87 m²/g,粒径约为3 μm。该工艺简单可行,为盐泥的综合利用提供了新的思路。     

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.