Leaching behavior of Cr(III) in stabilized/solidified soil

The leaching behavior of chromium was studied using batch leaching tests, surface complexation modeling and X-ray absorption near edge structure (XANES) spectroscopy. A contaminated soil sample containing 1330 mg-Cr kg(-1) and 25600 mg-Fe kg(-1) of dry soil was stabilized/solidified (S/S) with 10% cement, 25% cement, 10% lime and a mixture of 20% flyash and 5% lime. The XANES analysis showed that Cr(III) was the only Cr species in untreated soil and S/S-treated samples. The leachate Cr concentration determined using the toxicity characteristic leaching procedure (TCLP) was reduced from 5.18 mg l(-1) for untreated soil to 0.84 mg l(-1) for the sample treated with 25% cement. The Cr leachability in untreated and treated soil samples decreased dramatically as the pH increased from 3 to 5, remained at similar levels in the pH range between 5 and 10.5, and further decreased at pH>10.5. Modeling results indicated that the release of Cr(III) was controlled by adsorption on iron oxides at pH<10.5, and by precipitation of Ca(2)Cr(2)O(5).6H(2)O at pH>10.5.     

还原焙烧电镀污泥中的金属形态和浸出性

分别以煤粉和稻杆为还原剂对电镀污泥进行还原焙烧，并通过酸浸回收焙烧渣中的金属。研究了焙烧温度、焙烧时间和还原剂投加量对目标金属Cu浸出率的影响以及主要杂质金属的浸出性，并采用BCR逐级提取法分析了焙烧前后污泥中的金属形态分布。结果表明，当在电镀污泥中投加30％的煤粉在600℃下焙烧1h后Cu的浸出率达到97．78％，当投加50％的稻杆时浸出率为89．47％，而氧化焙烧后浸出率仅为37．71％；并且还原焙烧渣中多数杂质金属的浸出率较低，从而可以实现Cu与杂质金属的初步分离。氧化焙烧容易导致金属从易浸出的非残渣态向难浸出的残渣态转化，而还原焙烧则能抑制这种转化过程，金属形态是决定其浸出性的重要因素。     

Phosphorus release from ash, dried sludge and sludge residue from supercritical water oxidation by acid or base

Leaching of ash and dried sewage sludge were investigated and compared with the leaching results of sludge residue from supercritical water oxidation (SCWO). This article focuses on how the composition of ash and sludge residues influences the extraction of phosphate and heavy metals and if different treatment temperatures of the sludge effect the leachability. Results showed that acid leaching gave a higher release of phosphate than alkaline leaching for all ash and sludge residue samples. Also, alkaline leaching dissolved phosphate with a lower metal contamination than acid leaching. Furthermore, it was found that iron had a low release at both alkaline and acid leaching from ash and from SCWO residue. The difference in composition of ash and sludge residue samples had no significant influence on release of phosphate at high concentrations of acid. Phosphate release from ash, dried sludge at 300 degrees C and SCWO residue showed similar results at 1M acid leaching. However, it seems to be easier to release phosphate from the SCWO residue than from the ash at low acid concentrations. SCWO residue showed higher release than the other ashes at 0.5M HCl. Results for alkaline leaching showed higher release from ash at 1M NaOH than from SCWO residue or from dried sludge at 300 degrees C. The leaching of phosphate from dried sludge seems to be temperature dependent, as the dried sludge treated at higher temperature showed less release of phosphate. It was found that the pre-treatment of the ash may be important for better release of phosphate.     

Leaching of heavy metals and alkylphenolic compounds from fresh and dried sewage sludge

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP₁EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP₁EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.     

Assessment of the mechanical stability and chemical leachability of immobilized electroplating waste

The effectiveness of cement based treatment technology, in immobilizing chromium laden electroplating sludge was assessed by conducting toxicity characteristic leaching procedure (TCLP). The mechanical stability of the blocks was tested by measuring the compressive strength. Other leaching tests such as NEN 7341 test, ANS 16.1 and multiple TCLP (MTCLP) test conducted on select solidified blocks showed that chromium was immobilized by the binder studied. A linear relationship was obtained between the cumulative fraction of chromium leached (CFL) and square root of time in the solidified samples proving that diffusion is the controlling mechanism for leaching of chromium. The leachability indices (LI) obtained for the solidified materials using cement and cement-fly ash system (EPC6, EPFC6A and EPFC6B) satisfy the guidance value as per US NRC, which clearly indicates that chromium is well retained within the solid matrix. Chromium concentrations in the TCLP leachates of the above mix ratios were well within the regulatory level of United States Environmental Protection Agency (USEPA). Molecular characterization of the solidified material was carried out using Fourier transformation infra red (FTIR) technique.     

水泥对垃圾焚烧飞灰的固化处理试验研究

对垃圾焚烧飞灰的化学成分、重金属物质的含量及浸出浓度进行测试分析.结果表明,飞灰中Pb和Cr等重金属物质浸出量超过浸出毒性标准,因而被认为是危险废物,必须进行固化处理.还考察了水泥对焚烧飞灰中重金属物质固化的效果,研究表明当飞灰掺量适当时,重金属物质的固化效果良好.重金属物质通过物理固封、替代,沉淀反应和吸附等形式可固化进水泥水化产物结构中.     

水泥回转窑固化处理废弃重金属元素的实验研究

废弃的重金属化学试剂是一类危险的固体废物.通过在水泥回转窑中添加质量小于水泥质量的重金属化学试剂的实验研究表明(本实验添加质量约为水泥的0.1%):掺加化学试剂重金属元素后,各水泥熟料的XRD图谱相似,水泥熟料主要矿物相没有发生大的改变;重金属化学试剂的添加对水泥的7 d、28 d抗压强度的影响较小,符合国家标准;熟料试样在其水化28 d时各重金属的浸出量都很低,已低于工业固体废物浸出毒性鉴别标准规定的指标,由此表明利用水泥回转窑处理废弃化学试剂方法可行.     

Stabilization of heavy metals in municipal sewage sludge by freeze–thaw treatment with a blend of diatomite,FeSO4, and Ca(OH)2

In this work, the effects of diatomite with 15% FeSO₄?7H₂O and 7.5% Ca(OH)₂ on sludge stabilization were investigated using batch leaching tests. The influence of cell rupture caused by freezing and thawing on stabilization was also evaluated. The results indicated that the optimal diatomite percentage was 2%. Cell rupture by freezing and thawing reduced heavy metal leachability, followed by cell death and decrease of organic groups. The concentration of heavy metals in sludge leachate increased after cell rupture, indicating that the heavy metal leachability was reduced after freezing and thawings. Moreover, the stabilization effects were generally improved after freezing and thawing. As compared with the stabilization of the original sludge, the unstable fractions decreased and the residual fractions of the heavy metals increased in the stabilized sludge after cell rupture.

Implications: This study developed a method to stabilize heavy metals in municipal sewage sludge. Diatomite combined with FeSO₄·7H₂O and Ca(OH)₂ improved the treatment of sewage sludge contaminated by heavy metals. Cell lysis by freeze–thaw treatment reduced the risk of leaching heavy metals caused by cell death and decreased major organic groups in the sludge.     

Preparation and characterization of green bricks using pharmaceutical industrial wastes

This paper reports on recycling of industrial wastes (three pharmaceutical industrial sludges) into environmental friendly value-added materials. Stabilization/Solidification (S/S or bricks) process was applied to make a safer way for the utilization of pharmaceutical waste. The additives in this study include binders (cement, lime and bentonite) and strengthening material (pulverized fuel ash (PFA), silica fume and quarry dust) was used at different compositions. Bricks were cured for 28 days, and the following analysis-like compressive strength, leachability of heavy metals, mineralogical phase identity by X-ray diffraction (XRD) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermal behaviour by thermogravimetric-differential thermal analysis (TG-DTA) had done. All the bricks were observed to achieve the standard compressive strength as required for construction according to BIS standards. Metal concentration in the leachate has reached the dischargeable limits according to Brazilian standards. Results of this study demonstrate that production of bricks is a promising and achievable productive use of pharmaceutical sludge.     

Evaluation of the stability of arsenic immobilized by microbial sulfate reduction using TCLP extractions and long-term leaching techniques

An investigation was conducted to evaluate the stability or leachability of arsenic immobilized by microbial sulfate reduction. Anoxic solid-phase samples taken from a bioreactor previously used to treat metal and As contaminated water using sulfate reducing bacteria (SRB) were subjected to the toxicity characteristic leaching procedure (TCLP) and long-term column leaching tests. The results from TCLP experiments showed that the concentration of As leached from solid-phase sulfide material (SSM) samples after an 18 h extraction time was <300 microgl(-1), which is below the current maximum Australian TCLP leachate value for As, and thus would not be characterized as a hazardous waste. In terms of percent total As leached, this was equivalent to <8.5% for SSM samples initially containing 61.3 mgkg(-1) As. The levels of As extracted by the TCLP was found to be significantly lowered or underestimated in the presence of dissolved oxygen, with As concentrations increasing with decreasing headspace-to-leachant volume ratios. The concentration of As was also consistently higher in nitrogen purged extractions compared to those performed in air. This was attributed to the dissolution of Fe-sulfide precipitates and subsequent oxidation of Fe(II) ions and precipitation of ferric(hydr)oxides, resulting in the adsorption of soluble As and corresponding decrease in As concentrations. According to the experimental data, it is recommended that TCLP tests for As leachability should be performed at least in zero-headspace vessels or preferably under nitrogen to minimize the oxidation of Fe(II) to ferric(hydr)oxides. In long-term leaching studies (approximately 68 days), it was found that the low solubility of the SSM ensured that rate of release of As was relatively slow, and the resulting leachate concentrations of As were below the current Australian guideline concentration for arsenic in drinking water.     

锡冶炼含砷烟尘低温陶瓷固化技术

以锡冶炼过程中排放的含砷烟尘为研究对象,对浸出特性和低温陶瓷胶凝材料对其的固化效果进行了研究。结果表明,含砷烟尘As、Cu和Zn毒性浸出浓度分别为6 783、167和224 mg/L,严重超过国家毒性浸出鉴别标准值。其经低温陶瓷胶凝材料固化处理,当含砷烟尘掺量小于40%,自然养护3 d,As、Cu和Zn毒性浸出浓度急剧降低,且低于国家标准值。XRD和SEM分析表明,低温陶瓷胶凝材料在复合化学激发剂作用下,反应生成类沸石水化铝硅酸盐矿物(Al-O-Si);固化体中Ca-Fe-As-O盐是As固化的主要矿物相。Cu2+、Zn2+替换铝硅酸盐聚合物结构中的Na+、K+保持平衡电荷。胶凝材料水化产物填充于材料颗粒间,使其连接成一致密整体,有效降低了有害物质的毒性浸出浓度。     

电镀污泥的热处理特性以及对金属回收的影响

焙烧-酸浸法可有效回收电镀污泥中的有价金属,而污泥的热处理特性是决定能否采用焙烧预处理的重要因素。研究了氧化焙烧和还原焙烧对污泥成分和金属浸出性的影响,并对焙烧前后的污泥进行了金属形态分析和X射线衍射(XRD)分析。结果表明,焙烧预处理实现了污泥减量和金属富集;ES1经氧化焙烧后金属浸出率接近原泥,Cu的浸出率达99%;ES2的还原焙烧效果优于氧化焙烧,特别是Cu的浸出率超过97%,XRD分析发现,还原焙烧过程中金属Cu被还原为铁铜合金;2种焙烧均造成了ES3中目标金属Ni的浸出率的降低;金属浸出性的下降与残渣态的形成有关。     

Arsenic species and leachability in the fronds of the hyperaccumulator Chinese brake (Pteris vittata L.)

Arsenic speciation is important not only for understanding the mechanisms of arsenic accumulation and detoxification by hyperaccumulators, but also for designing disposal options of arsenic-rich biomass. The primary objective of this research was to understand the speciation and leachability of arsenic in the fronds of Chinese brake (Pteris vittata L.), an arsenic hyperaccumulator, with an emphasis on the implications for arsenic-rich biomass disposal. Chinese brake was grown for 18 weeks in a soil spiked with 50 mg As kg(-1) as arsenate (AsO4(3-)), arsenite (AsO3(3-)), dimethylarsinic acid (DMA), or methylarsonic acid (MMA). Plant samples were extracted with methanol/water (1:1) and arsenic speciation was performed using high performance liquid chromatography coupled with atomic fluorescence spectrometry. The impacts of air-drying on arsenic species and leachability in the fronds were examined in the laboratory. After 18 weeks, water-soluble arsenic in soil was mainly present as arsenate with little detectable organic species or arsenite regardless of arsenic species added to the soil. However, arsenic in the fronds was primarily present as inorganic arsenite with an average of 94%. Arsenite re-oxidation occurred in the old fronds and the excised dried tissues. Arsenic species in the fronds were slightly influenced by arsenic forms added to the soil. Air-drying of the fronds resulted in leaching of substantial amounts of arsenic. These findings can be of significance when looking at disposal options of arsenic-rich biomass from the point of view of secondary contamination.     

Fractionation and leachability of Fe,Zn, Cu and Ni in the sludge from a sulphate-reducing bioreactor treating metal-bearing wastewater

This work presents and discusses experimental results on the characterisation and metal leaching potential of a biogenic, metal-rich sulphidic sludge, generated in a sulphate-reducing bioreactor, operated to treat acidic synthetic solutions bearing Fe, Zn, Ni and Cu. The sustainability of the metal removal bioprocess strongly depends on the fate of the sludge. To propose appropriate management practices, a detailed characterisation of the sludge is necessary. The granulometry, chemical composition and mineralogy of the sludge were initially determined. The mobility of the metals was assessed via a modified Tessier experimental procedure. The leachability of the sludge metal content was determined via a standard compliance method (EN 12457-2) and experiments designed to evaluate the effect of pH and time on metal leaching from the sludge. The sludge metal content sums up to 69.5% dw, namely iron (14.8%), zinc (18.7%), nickel (17.7%) and copper (18.2%) and, based on the criteria set by European Union, the sludge is characterised as hazardous and inappropriate for landfilling without any pretreatment. The sludge consists mainly of very fine poorly crystalline aggregates of Fe, Zn, Cu and Ni sulphides. The fine grain size, the poorly crystalline structure and the oxidation of sulphide upon exposure to water/air render the high metal content of the sludge recoverable.     

Effects of injected activated carbon and solidification treatment on the leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans from air pollution control residues of municipal waste incineration

To assess the effectiveness of the injected activated carbon, cement, and sulfur-containing chelating agent in controlling polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) release from the surface of air pollution control (APC) residues, this study examined the leachability of PCDD/Fs from APC residues generated by municipal solid waste incinerators. Results showed that PCDD/Fs were stably retained in the APC residues when the samples were leached with acetic acid solution. Highly chlorinated PCDD/F homologues (i.e., hepta- and octa-CDDs and CDFs) were relatively easy to leach. The leaching percentages of PCDD/Fs from raw APC residue samples containing activated carbon were smaller than those from samples without activated carbon, especially when n-hexane was used as the leachant. These results indicate that the flue gas injected activated carbon not only controls PCDD/F emissions, but also suppresses the leachability of PCDD/Fs from the APC residues. Solidification/stabilization (S/S) processes with 30wt% cement and 5wt% sulfur-containing agent can additionally decrease the leachability of PCDD/Fs with humic acid. Using n-hexane as the leachant, S/S processes increased the leachability of PCDD/Fs. Various low chlorinated PCDD/F congeners were moreover leached out of the APC residue samples, markedly increasing the leachate toxicity. The enhancement of leachability and toxicity owing to S/S processes may negatively impact the environment when APC residues are exposed to nonpolar organic solvents.     

Fate of zinc in an electroplating sludge during electrokinetic treatments

Chemical structure of zinc in the electrokinetic treatments of an electroplating sludge has been studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The least-square fitted XANES spectra indicate that the main zinc compounds in the sludge were ZnCO(3) (75%), ZnOSiO(2) (17%) and Zn(OH)(2) (7%). Zinc in the sludge possessed a Zn-O bond distance of 2.07 A with a coordination number (CN) of 5. In the second shells, the bond distance of Zn-(O)-Si was 3.05 A (CN=2). An increase of Zn-(O)-Si (0.05 A) with a decrease of its CN (from 5 to <1) was found in the early stage of the electrokinetic treatment. Prolong the electrokinetic treatment time to 180 min, about 34% of Zn(II) was dissolved into the aqueous phase and about 68% of Zn(II) in the sludge (or 23% of total zinc) was migrated to the cathode under the electric field (5 V cm(-1)). The dissolution and electromigration rates of Zn(II) in the sludge were 1.0 and 0.6 mmol h(-1)g(-1) sludge, respectively during the electrokinetic treatment. This work also exemplifies the utilization of in situ EXAFS and XANES for revealing speciation and possible reaction pathways during the course of zinc recycling from the sludge by electrokinetic treatments.     

Leaching characteristics of stabilized/solidified fly ash generated from ash-melting plant

This study was designed to elucidate the leaching characteristics of stabilized/solidified (S/S) fly ash generated by ash-melting. For this study, pH-dependent leaching tests, sequential extraction procedures, and column leaching tests were carried out. The pH-dependent leaching test results for Pb, Cu, and Zn showed that the heavy metal concentrations in the high-pH range were lower than the predicted values for hydroxide and carbonate. During sequential extraction, Cu and Pb were principally distributed in the S/S ashes' organic matter fraction in the chelating agent, suggesting that metals bind to the chelating agent. The percentage of the water-soluble fraction for Pb and Cu was low (<0.2 %). The fly ashes treated with a chelating agent and cement had low leachability potential for metals in the high-pH range. Column tests for S/S fly ashes showed that two leaching stages were distinguishable: one for short time, corresponding to faster metal leaching, and another for the leaching rate. Kinetic speciation was then applied to data obtained from column leaching tests. The first-order reaction/diffusion model showed a better fit for Ca, Pb, and Cu, suggesting that the initial dissolution of soluble compounds, such as metal chloride, was controlled by the first-order reaction (surface wash off). Subsequently, insoluble compounds such as hydroxide or carbonate might penetrate into the porous matrix by diffusion.     

The leachability and chemical speciation of selected trace elements in fly ash from coal combustion and refuse incineration

A laboratory leaching test has been used to predict the potential mobility of As, Se, Pb and Cd in landfilled fly ash produced by coal combustion and refuse incineration. These waste residues also formed the basis of a speciation study in which the valency states of As and Se and the chemical forms of Pb and Cd have been determined. Selenium displayed the greatest leachability in each ash type, despite being present at relatively low concentrations in both materials. Substantial amounts of other trace elements were also leached, particularly Pb and Cd from refuse ash and As from coal ash. Chemical associations of Pb and Cd were examined by a sequential extraction procedure. In coal fly ash, both elements were mostly present in the residual fraction, while in refuse ash these elements were mainly associated with the exchangeable fraction. Water-soluble extracts of coal fly ash contained As exclusively as As(V); high background interference prevented the detection of water-soluble As in refuse ash. Selenium was present largely as Se(IV) in aqueous extracts of both ash types. The value of speciation techniques and leaching tests as predictors of environmental behaviour is discussed in conjunction with results of routine trace element determinations and plant uptake studies.     

Arsenic contaminated site at an abandoned copper smelter plant: waste characterization and solidification/stabilization treatment

A preliminary survey of an arsenic contaminated site from an abandoned copper smelting facility and feasibility study of using solidification/stabilization (S/S) process to treat the contaminant waste were undertaken. It was found that the waste, located in the three-flue gas discharge tunnels, contained 2-40% arsenic. The pH of the contaminated waste is extremely low (ranging from 1.8 to 3.6). The X-ray diffraction evidence indicates that the arsenic particles present in the flue gas mainly exist as As(III), or As(2)O(3). The total amount of arsenic contaminated waste is estimated to be 700 ton in the studied area. About 50% of the particle sizes are less than 2 mm. Arsenic is easily extracted from wastes with a variety of leaching solutions. In order to meet the arsenic leaching standard of the toxicity characteristic leaching procedure (TCLP), an extremely high cement dosage is required in the S/S process (cement/waste weight ratio>6). The waste with lower particle size having higher specific surface area exhibits somewhat positive effect on the S/S performance. The use of fly ash from municipal waste incinerators, in conjunction with the reduced amount of cement, is able to meet the TCLP arsenic and lead standards. The use of lime alone could meet the TCLP arsenic standard, but lead leaching concentrations exceeded leaching Pb standard. The results of semi-dynamic leaching tests of some solidified samples indicate higher accumulated arsenic leaching concentrations after only a few leachant renewals.     

Arsenic and copper stabilisation in a contaminated soil by coal fly ash and green waste compost

In situ metal stabilisation by amendments has been demonstrated as an appealing low-cost remediation strategy for contaminated soil. This study investigated the short-term leaching behaviour and long-term stability of As and Cu in soil amended with coal fly ash and/or green waste compost. Locally abundant inorganic (limestone and bentonite) and carbonaceous (lignite) resources were also studied for comparison. Column leaching experiments revealed that coal fly ash outperformed limestone and bentonite amendments for As stabilisation. It also maintained the As stability under continuous leaching of acidic solution, which was potentially attributed to high-affinity adsorption, co-precipitation, and pozzolanic reaction of coal fly ash. However, Cu leaching in the column experiments could not be mitigated by any of these inorganic amendments, suggesting the need for co-addition of carbonaceous materials that provides strong chelation with oxygen-containing functional groups for Cu stabilisation. Green waste compost suppressed the Cu leaching more effectively than lignite due to the difference in chemical composition and dissolved organic matter. After 9-month soil incubation, coal fly ash was able to minimise the concentrations of As and Cu in the soil solution without the addition of carbonaceous materials. Nevertheless, leachability tests suggested that the provision of green waste compost and lignite augmented the simultaneous reduction of As and Cu leachability in a fairly aggressive leaching environment. These results highlight the importance of assessing stability and remobilisation of sequestered metals under varying environmental conditions for ensuring a plausible and enduring soil stabilisation.