Removal of copper,chromium, and arsenic from CCA-C treated wood by EDTA extraction

Ethylenediaminetetracetic acid (EDTA) is one of the most common chelators used to bind the metal ions in extremely stable complexes in heavy metal contaminated soils and thus to remediate such substrates. EDTA forms water soluble complexes with many metal ions and it is used to release the various metals. In this study, EDTA extraction of copper, chromium, and arsenic from chromated copper arsenate (CCA-C) treated wood was evaluated using batch leaching experiments. CCA-treated wood samples were extracted with eight different concentrations of EDTA for 4, 8, 18, and 24 h at room temperature. Exposing CCA-treated chips and sawdust to EDTA extraction enhanced removal of CCA components compared with extraction by deionized water. Grinding CCA-treated wood chips into 40-mesh sawdust provided greater access to and removal of CCA components. Extraction with 1% EDTA solution for 24 h removed 60% copper, 13% chromium, and 25% arsenic from treated chips. EDTA extraction of treated sawdust samples resulted in 93% copper, 36% chromium, and 38% arsenic removal. CCA leaching from treated wood blocks was also evaluated according to modified AWPA E11-99 standard test method of determining the leachability of wood preservatives. Leaching of CCA components from treated wood blocks with 1% EDTA solution for 14 days caused more copper leaching compared to leaching with deionized water. Leaching with 1% EDTA for 14 days removed 53% copper from the blocks whereas 14% copper was leached from the blocks with deionized water. The results suggest that EDTA extraction removes significant quantities of copper from CCA-treated wood. Thus, EDTA could be important in the remediation of wood waste treated with the newest formulations of organometalic copper compounds and other water-borne wood preservatives containing copper.     

Designing a purification process for chromium-, copper- and arsenic-contaminated wood

The disposal of chromated copper arsenate (CCA)-treated wood is becoming a serious problem in many countries due to increasing levels of contamination by the hazardous elements, chromium, copper and arsenic. The present experiment was conducted as a preliminary step toward one-step solvent extraction of CCA-treated wood. Because chromium, copper and arsenic have different chemical characteristics, it is best to consider them separately prior to designing a one-step extraction process. As a basis, various two-step extraction processes were first designed and tested experimentally to determine feasibility. Among these combinations, the treatment combining oxalic acid as the 1st step and a sodium oxalate solution under acidic conditions (pH 3.2) as the 2nd step was found to be an effective way of extracting CCA elements from treated wood. Extraction efficiency reached 100% for arsenic and chromium and 95.8% for copper after a 3-h sodium oxalate treatment, following a 1-h pre-extraction process with oxalic acid. On the other hand, the same combination under alkaline conditions (pH 11.2) during the 2nd step was ineffective for copper removal, indicating that pH plays an important role in complexation with sodium oxalate solution. The present results suggest that the extraction of CCA elements using a combination of oxalic acid and acidic sodium oxalate solution is a promising basis for application to a one-step extraction method.     

Improving the two-step remediation process for CCA-treated wood: Part I. Evaluating oxalic acid extraction

In this study, three possible improvements to a remediation process for chromated-copper-arsenate- (CCA) treated wood were evaluated. The process involves two steps: oxalic acid extraction of wood fiber followed by bacterial culture with Bacillus licheniformis CC01. The three potential improvements to the oxalic acid extraction step were (1) reusing oxalic acid for multiple extractions, (2) varying the ratio of oxalic acid to wood, and (3) using a noncommercial source of oxalic acid such as Aspergillus niger, which produces oxalic acid as a metabolic byproduct. Reusing oxalic acid for multiple extractions removed significant amounts of copper, chromium, and arsenic. Increasing the ratio of wood to acid caused a steady decline in metal removal. Aspergillus niger removed moderate amounts of copper, chromium, and arsenic from CCA-treated wood. Although A. niger was effective, culture medium costs are likely to offset any benefits. Repeated extraction with commercial oxalic acid appears to be the most cost-effective method tested for the two-step process.     

Improving the two-step remediation process for CCA-treated wood: Part II. Evaluating bacterial nutrient sources

Remediation processes for recovery and reuse of chromated-copper-arsenate- (CCA) treated wood are not gaining wide acceptance because they are more expensive than landfill disposal. One reason is the high cost of the nutrient medium used to culture the metal-tolerant bacterium, Bacillus licheniformis, which removes 70-100% of the copper, chromium, and arsenic from CCA-treated southern yellow pine (CCA-SYP) in a two-step process involving oxalic acid extraction and bacterial culture. To reduce this cost, the nutrient concentration in the culture medium and the ratio of wood to nutrient medium were optimized. Maximum metal removal occurred when B. licheniformis was cultured in 1.0% nutrient medium and at a wood to nutrient medium ratio of 1:10. Also, malted barley, an abundant by-product of brewing, was evaluated as an alternative nutrient medium. Tests were done to determine absorption of metals by barley, and the results indicate that the barley acted as a biosorbent, removing heavy metals from the liquid culture after their release from CCA to SYP. For comparison, tests were also performed with no nutrient medium. Following bacterial remediation, 17% copper and 15% arsenic were removed from an aqueous slurry of CCA-SYP (no medium). When oxalic acid extraction preceded the aqueous bacterial culture, 21% copper, 54% chromium, and 63% arsenic were removed. The two-step process (oxalic acid extraction and bacterial culture with nutrient medium) appears to be an effective, yet costly, way to remove metals.     

Rapid-extraction oxidation process to recover and reuse copper chromium and arsenic from industrial wood preservative sludge

Chromated copper arsenate (CCA) wood preservative can form insoluble sludges when the hexavalent chromium component is reduced by wood extractives, wood particles and preservative additives in the solution. This sludge accumulates in treating solution work tanks, sumps and in-line filters and must be disposed of as hazardous wastes by waste disposal companies at high costs. A number of commercial sludges were investigated and found to contain 18-94% copper, chromium and arsenic as oxides combined with sand, oil, wood particles, additives and wood extractives. We have developed a multi-stage recycling process whereby approximately 97% of the CCA components are recovered from the sludge. It involves extraction with sodium hypochlorite to remove and oxidize chromium (more than 90%) and extract most of the arsenic (approx. 80%) followed by extraction of the copper and remaining arsenic and chromium with phosphoric acid. The phosphoric acid extract contains some trivalent chromium, which is subsequently oxidized by sodium hypochlorite. The combined oxidized extract containing CrVI, CuII and AsV was compatible with CCA treating solutions and could be re-used commercially for treating wood without having a significant effect on the preservative fixation rate or the leach resistance of the treated wood. A cost analysis showed that the economic savings from recovery of CCA chemicals and reduced landfill costs exceeded the variable costs for materials and energy for the process by as much as Can $966 per tonne of sludge if sodium sulfite can be acquired in bulk quantities for the process.     

Evaluation of commercial landscaping mulch for possible contamination from CCA

Wood treated with chromated copper arsenate (CCA) is found in construction and demolition (C&D) debris, and a common use for wood recycled from C&D debris is the production of mulch. Given the high metals concentrations in CCA-treated wood, a small fraction of CCA-treated wood can increase the metal concentrations in the mulch above regulatory thresholds. The objective of this study was to determine the extent of contamination of CCA-treated wood in consumer landscaping mulch and to determine whether visual methods or rapid X-ray fluorescence (XRF) technology can be used to identify suspect mulch. Samples were collected throughout the State of Florida (USA) and evaluated both visually and chemically. Visual analysis focused on documenting wood-chip size distribution, whether the samples were artificially colored, and whether they contained plywood chips which is an indication that the sample was, in part, made from recycled C&D wood. Chemical analysis included measurements of total recoverable metals, leachable metals as per the standardized synthetic precipitation leaching procedure (SPLP), and XRF analysis. Visual identification methods, such as colorant addition or presence of plywood, were found effective to preliminarily screen suspect mulch. XRF analysis was found to be effective for identifying mulch containing higher than 75 mg/kg arsenic. For mulch samples that were not colored and did not contain evidence of C&D wood, none exceeded leachable metal concentrations of 50 microg/L and only 3% exceeded 10 mg/kg for recoverable metals. The majority of the colored mulch made from recycled C&D wood contained from 1% to 5% CCA-treated wood (15% maximum fraction) resulting in leachable metals in excess of 50 microg/L and total recoverable metals in excess of 10 mg/kg. The maximum arsenic concentration measured in the mulch samples evaluated was 230 mg/kg, which was above the Florida residential direct exposure regulatory guideline of 2.1 mg/kg.     

赤泥制备含钛聚硅酸铝铁及亚甲基蓝溶液的混凝脱色

以拜耳法赤泥为原料、Na Cl为助溶剂,采用酸浸法溶出赤泥中的铁、铝元素,再与硅酸钠、硫酸氧钛反应制备出高效混凝剂含钛聚硅酸铝铁(T-PSAF),并将其用于模拟亚甲基蓝印染废水的脱色。实验结果表明:在硫酸浓度为8 mol/L、液固比(硫酸体积与干赤泥质量之比)为14 m L/g、酸浸温度为80℃、酸浸时间为80 min、Na Cl加入量为0.10 g/g(以干赤泥计)的优化酸浸条件下,铁、铝的浸出率分别为88.25%和73.21%;在n(Fe+Al)∶n(Ti)∶n(Si)=0.3∶0.3∶1、熟化p H为4~5、熟化时间为2 h、混凝剂加入量为25 m L/L的优化混凝条件下,初始亚甲基蓝质量浓度为10 mg/L的废水的脱色率可达87.1%,而当初始亚甲基蓝质量浓度增至150~200 mg/L时废水脱色率可达99%以上。     

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.     

Comparison of leaching characteristics of heavy metals from bottom and fly ashes in Korea and Japan

The objective of this research was to compare the leaching characteristics of heavy metals such as cadmium, chromium, copper, nickel, lead, etc., in Korean and Japanese municipal solid waste incineration (MSWI) ash. The rate of leaching of heavy metal was measured by KSLT and JTL-13, and the amount of heavy metals leached was compared with the metal content in each waste component. Finally, bio-availability testing was performed to assess the risks associated with heavy metals leached from bottom ash and fly ash. From the results, the value of neutralization ability in Japanese fly ash was four times higher than that in Korean fly ash. The reason was the difference in the content of Ca(OH)(2) in fly ash. The amount of lead leached exceeded the regulatory level in both Japanese and Korean fly ash. The rate of leaching was relatively low in ash with a pH in the range of 6-10. The bio-availability test in fly ash demonstrated that the amount of heavy metals leached was Pb>Cd>Cr, but the order was changed to Pb>Cr>Cd in the bottom ash. The leaching concentration of lead exceeded the Japanese risk level in all fly ashes from the two countries, but the leaching concentration of cadmium exceeded the regulatory level in Korean fly ash only.     

废弃SCR催化剂中钒和钨的浸出及回收

采用NaOH溶液一次性浸出废弃SCR催化剂中的钒和钨,并用硫酸对浸出液进行除杂,再利用NH4Cl和硫酸分步对浸出液中的钒和钨进行沉淀回收。在NaOH质量分数40%、液固比8、浸出时间4 h、浸出温度90℃的最佳碱浸条件下,钒和钨的浸出率分别达到90.44%和84.49%。除杂过程的铝去除率达到100%,硅去除率达到77.56%。在沉钒pH为8.0、n(NH_4~+)∶n(V)为4的最佳沉钒条件下,钒回收率达到82.79%。在n(SO_4~(2-))∶n(W)为2的最佳沉钨条件下,钨回收率达到76.41%。     

CCA-treated wood disposed in landfills and life-cycle trade-offs with waste-to-energy and MSW landfill disposal

Chromated copper arsenate (CCA)-treated wood is a preservative treated wood construction product that grew in use in the 1970s for both residential and industrial applications. Although some countries have banned the use of the product for some applications, others have not, and the product continues to enter the waste stream from construction, demolition and remodeling projects. CCA-treated wood as a solid waste is managed in various ways throughout the world. In the US, CCA-treated wood is disposed primarily within landfills; however some of the wood is combusted in waste-to-energy (WTE) facilities. In other countries, the predominant disposal option for wood, sometimes including CCA-treated wood, is combustion for the production of energy. This paper presents an estimate of the quantity of CCA-treated wood entering the disposal stream in the US, as well as an examination of the trade-offs between landfilling and WTE combustion of CCA-treated wood through a life-cycle assessment and decision support tool (MSW DST). Based upon production statistics, the estimated life span and the phaseout of CCA-treated wood, recent disposal projections estimate the peak US disposal rate to occur in 2008, at 9.7 million m(3). CCA-treated wood, when disposed with construction and demolition (C&D) debris and municipal solid waste (MSW), has been found to increase arsenic and chromium concentrations in leachate. For this reason, and because MSW landfills are lined, MSW landfills have been recommended as a preferred disposal option over unlined C&D debris landfills. Between landfilling and WTE for the same mass of CCA-treated wood, WTE is more expensive (nearly twice the cost), but when operated in accordance with US Environmental Protection Agency (US EPA) regulations, it produces energy and does not emit fossil carbon emissions. If the wood is managed via WTE, less landfill area is required, which could be an influential trade-off in some countries. Although metals are concentrated in the ash in the WTE scenario, the MSW landfill scenario releases a greater amount of arsenic from leachate in a more dilute form. The WTE scenario releases more chromium from the ash on an annual basis. The WTE facility and subsequent ash disposal greatly concentrates the chromium, often oxidizing it to the more toxic and mobile Cr(VI) form. Elevated arsenic and chromium concentrations in the ash leachate may increase leachate management costs.     

Factors affecting sodium hypochlorite extraction of CCA from treated wood

Significant amounts of chromated copper arsenate (CCA) treated wood products, such as utility poles and residential construction wood, remain in service. There is increasing public concern about environmental contamination from CCA-treated wood when it is removed from service for reuse or recycling, placed in landfills or burned in commercial incinerators. In this paper, we investigated the effects of time, temperature and sodium hypochlorite concentration on chromium oxidation and extraction of chromated copper arsenate from CCA-treated wood (Type C) removed from service. Of the conditions evaluated, reaction of milled wood with sodium hypochlorite for one hour at room temperature followed by heating at 75 °C for two hours gave the highest extraction efficiency. An average of 95% Cr, 99% Cu and 96% As could be removed from CCA-treated, milled wood by this process. Most of the extracted chromium was oxidized to the hexavalent state and could therefore be recycled in a CCA treating solution. Sodium hypochlorite extracting solutions could be reused several times to extract CCA components from additional treated wood samples.     

Finished leather waste chromium acid extraction and anaerobic biodegradation of the products

Due to the amounts of chromium in the leachate resulting from leather leaching tests, chromium sulfate tanned leather wastes are very often considered hazardous wastes. To overcome this problem, one option could be recovering the chromium and, consequently, lowering its content in the leather scrap. With this objective, chromium leather scrap was leached with sulfuric acid solutions at low temperature also aiming at maximizing chromium removal with minimum attack of the leather matrix. The effects of leather scrap dimension, sulfuric acid and sodium sulfate concentration in the solutions, as well as extraction time and temperature on chromium recovery were studied, and, additionally, organic matrix degradation was evaluated. The best conditions found for chromium recovery were leather scrap conditioning using 25 mL of concentrated H₂SO₄/L solution at 293 or 313 K during 3 or 6 days. Under such conditions, 30–60 ± 5% of chromium was recovered and as low as 3–6 ± 1% of the leather total organic carbon (TOC) was dissolved. Using such treatment, the leather scrap area and volume are reduced and the residue is a more brittle material showing enhanced anaerobic biodegradability. Although good recovery results were achieved, due to the fact that the amount of chromium in eluate exceeded the threshold value this waste was still hazardous. Thus, it needs to be methodically washed in order to remove all the chromium de-linked from collagen.     

Leachability of heavy metals from copper blasting grit waste

This investigation presents the results of leaching tests, using the multiple-batch procedure, on cadmium, zinc, copper, lead, and chromium from copper blasting grit waste generated from a shipbuilding and repair company in Bahrain. The leaching test results have demonstrated that the metals tested were generally released in low concentrations except for copper and zinc. Metal leachability appeared to be dependent upon the pH and composition of the leaching medium.     

Conversion of CCA-treated wood to ethanol: a method to reduce leaching of metals from disposed treated wood prior to disposal

The objective of this paper is to evaluate the feasibility of producing ethanol from CCA-treated wood that is highly leachable. Following the initial tests, CCA-treated wood was hydrolysed and fermented and the results showed not only that ethanol was produced during the fermentation process but that metals were taken up by the yeast. Toxicity characteristic leaching procedure tests of the hydrolysed wood leached less than 4 mg/L of As while minimal amounts of Cr and Cu remained in the hydrolysed wood which makes landfilling of hydrolysed wood acceptable and less hazardous. A slightly lower amount of ethanol from CCA-treated than untreated wood was produced (6 and 7 g/L, respectively). In general, it suggests that production of ethanol as a source of energy from a hazardous waste (CCA-treated wood) is feasible.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

Evaluation of heavy metal leaching from spent household batteries disposed in municipal solid waste

Batch leaching tests and simulated landfill lysimeter tests were performed to evaluate the contents of heavy metals leached from spent batteries in the municipal solid waste. The toxicity characteristic leaching procedure was utilized to perform the batch leaching tests of 36 spent batteries. Four lysimeters were prepared with battery contents ranging from 0% to 100% by weight for column tests, and the experiments were performed at ambient temperature. The age of all the batteries used in the study ranged from freshly disposed up to approximately 3 years old. The results from the batch tests showed that the type of battery influenced the heavy metal concentrations in the leached solutions. The lysimeter experiment results illustrated that at lower pH levels more metals are leached than at higher pH levels. The increasing amount of batteries disposed in landfills can contribute to the leaching of more metals, especially Mn and Zn, into the environment. These results indicate that the direct disposal of spent household batteries into a MSW landfill can increase the heavy metal contents in the landfill leachate.     

Influence of corn steep liquor and glucose on colonization of control and CCB (Cu/Cr/B)-treated wood by brown rot fungi

There are increasing problems with regard to the disposal of treated wood waste. Due to heavy metals or arsenic in impregnated wood waste, burning and landfill disposal options are not considered to be environmentally friendly solutions for dealing with this problem. Extraction of the heavy metals and recycling of the preservatives from the wood waste is a much more promising and environmentally friendly solution. In order to study the scale up of this process, copper/chromium/boron-treated wood specimens were exposed to copper tolerant (Antrodia vaillantii and Leucogyrophana pinastri) and copper sensitive wood decay fungi (Gloeophyllum trabeum and Poria monticola). Afterwards, the ability of fungal hyphae to penetrate and overgrow the wood specimens was investigated. The fungal growths were stimulated by immersing the specimens into aqueous solution of glucose or corn steep liquor prior to exposure to the fungi. The fastest colonization of the impregnated wood was by the copper tolerant A. vaillantii. Addition of glucose onto the surface of the wood specimens increased the fungi colonization of the specimens; however, immersion of the specimens into the solution of corn steep liquor did not have the same positive influence. These results are important in elucidating copper toxicity in wood decay fungi and for using these fungi for bioremediation of treated wood wastes.