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.     

汞矿区汞污染土壤的淋洗修复

以贵州省铜仁市汞矿区汞污染土壤为研究对象,分别采用KI、Na_2S_2O_3、乙二胺四乙酸、柠檬酸、酒石酸、十二烷基硫酸钠溶液对其进行淋洗修复,筛选出合适的淋洗剂,优化了淋洗条件,并探索了淋洗液的处理方法。实验结果表明:对该土壤淋洗效果最好的淋洗剂为Na_2S_2O_3,最佳淋洗条件为Na_2S_2O_3浓度0.01 mol/L、固液比(g/m L)1∶5、淋洗时间4 h、淋洗次数1次,在此条件下土壤中总汞的淋洗率为13.41%,有效态汞含量可降至原来的61.54%;Na2S对淋洗液中的汞具有较好的去除效果,每升淋洗液加入0.6 g Na_2S处理后,即可满足GB8978—1996《污水综合排放标准》。     

Case study: Using soil washing/leaching for the removal of heavy metal at the twin cities army ammunition plant

COGNIS TERRAMET® soil leaching and Bescorp soil washing systems have been successfully combined to remediate an ammunition test burn area at the Twin Cities Army Ammunition Plant (TCAAP), New Brighton, Minnesota. This cleanup is the first in the country to successfully combine these two technologies, and it offers a permanent solution to heavy metal remediation. Over 20,000 tons of soil were treated in the project. The cleaned soil remained on-site, and the heavy metal contaminants were removed, recovered, and recycled. Eight heavy metals were removed from the contaminated soil achieving the very stringent cleanup criteria of <175 ppm for residual lead and achieving background concentrations for seven other project metals (antimony, cadmium, chromium, copper, mercury, nickel, and silver). Initial contaminant levels were measured as high as 86,000 ppm lead and 100,000 ppm copper, with average concentrations over 1,600 ppm each. In addition, both live and spent ordnance were removed in the soil treatment plant to meet the cleanup criteria. By combining soil washing and leaching, COGNIS and Bescorp were able to assemble a process which effectively treats all the soil fractions so that all soil material can be returned on-site, no wastewater is generated, and the heavy metals are recovered and recycled. No hazardous waste requiring landfill disposal was generated during the entire remedial operation.     

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.     

Electroremediation part II: A study of the movement of heavy metals during an electroremediation process in Andisol soil

In the Summer 2004 issue of Remediation, the authors presented a study of the influence of buffering behavior in contaminated Andisol soil. This article, Part II, expands on this research by presenting the results of laboratory tests conducted to study the movement of heavy metals in contaminated Andisol soil during the first stage of an electrochemical remediation process. The analysis was performed on the soil after treatment and also on the washing solutions collected during the first four hours. In order to analyze the effectiveness of fast and simple techniques for monitoring the electroremediation process, computer‐aided modeling of speciation in the soil solution was performed in connection with the remediation treatment. The results show that the metals moved mainly as positive species in the soil and later occurred as insoluble forms relative to the pH value in the washing solution from the cathode chamber. © 2005 Wiley Periodicals, Inc.     

Removal of Cr(VI) from contaminated soil by electrokinetic remediation

A new process for the removal of hexavalent chromium [Cr(VI)] contaminated soil is described. The process provides for an efficient removal of anionic chemicals from contaminated soils. Chromate anions were removed from the soil to the anodic reservoir by the moving force of electromigration. In this process, the chromate anions that accumulate in the anodic reservoir are simultaneously eliminated by using a column packed adsorbent. The adsorbent (immobilized tannin) used was chemically incorporated into cellulose. Cr(VI) was found to be adsorbed to this adsorbent efficiently. In the electrokinetic process, the pH of the aqueous solution in the anodic reservoir was decreased by the electrolysis of water. In the present study, the pH of the solution in the anodic reservoir is maintained at pH 6 by the addition of an aqueous alkaline solution during the electrokinetic process. The advantage of pH control is that it promotes the release of Cr(VI) from the soil by electromigration, thus permitting the maximum adsorption of Cr(VI) on the immobilized tannin. Simultaneous collection of Cr(VI) from the anodic reservoir leads to the protection from secondary contamination with Cr(VI).     

Evaluation of the optimal washing conditions for dioxin-contaminated soils from the circumference of an incinerator

 The optimal soil-washing conditions for dioxins were estimated on a soil sample from the circumference of an incinerator in Nose City, Osaka, Japan. The solvents ethanol, methanol, and acetone, together with a surfactant (100% of each) could extract 40% of the dioxins from contaminated soil at room temperature. From among these solvents, ethanol was chosen for a study on how to optimize the extraction conditions because of its low toxicity and its economic advantages. The time-course of the agitation showed that the extraction rate increased for 1 min, and thereafter the rate decreased. Therefore, the agitation time was fixed at 1 min. To estimate the effect of temperature on the extraction rate, the extraction temperature was changed. The amount of dioxins extracted was largest at the boiling point of ethanol (78.3°C), giving about 76% extraction. Furthermore, at this temperature, almost 100% of the dioxins in the contaminated soil were extracted when the ratio of water to ethanol was 20%. Received: March 6, 2002 / Accepted: September 9, 2002     

Use of biosurfactants from urban wastes compost in textile dyeing and soil remediation

A compost isolated humic acid-like (cHAL) material was pointed out in previous work for its potential as auxiliary in chemical technology. Its potential is based on its relatively low 0.4gL(-1) critical micellar concentration (cmc) in water, which enables cHAL to enhance the water solubility of hydrophobic substances, like phenanthrene, when used at higher concentrations than 0.4gL(-1). This material could be obtained from a 1:1 v/v mixture of municipal solid and lignocellulosic wastes composted for 15 days. The compost, containing 69.3% volatile solids, 39.6% total organic C and 21C/N ratio, was extracted for 24h at 65 degrees C under N2 with aqueous 0.1molL(-1) NaOH and 0.1molL(-1) Na4P2O7, and the solution was acidified to separate the precipitated cHAL in 12% yield from soluble carbohydrates and other humic and non-humic substances. In this work two typical applications of surfactants, i.e., textile dyeing (TD) and soil remediation by washing (SW), were chosen as grounds for testing the performance of the cHAL biosurfactant against the one of sodium dodecylsulfate (SDS), which is a well established commercial synthetic surfactant. The TD trials were carried out with nylon 6 microfiber and a water insoluble dye, while the SW tests were performed with two soils contaminated by polycyclic aromatic hydrocarbons (PAH) for several decades. Performances were rated in the TD experiments based on the fabric colour intensity (DeltaE) and uniformity (sigmaDeltaE), and in the SW experiments based on the total hydrocarbons concentration (CWPAH) and on the residual surfactant (Cre) concentrations in the washing solution equilibrated with the contaminated soils. The results show that both cHAL and SDS exhibit enhanced performance when applied above their cmc values. However, while in the TD case a significant performance effect was observed at the surfactants cmc value, in the SW case the required surfactants concentration values were equivalent to 25-125xcmc for cHAL and to 4-22xcmc for SDS. The vis-a-vis comparison of the two surfactants gave the following results: in the TD case the cHAL biosurfactant at 0.4gL(-1) yields good colour intensity and equal colour uniformity as SDS at 5gL(-1), in the SW case cHAL was found to enhance CWPAH by a factor of 2-4 relative to SDS with one soil, whereas with the other soil the two surfactants behaved similarly. The Cre data, however, showed that both soils absorbed by far more SDS (68-95%) than cHAL (12-54%). The results point out intriguing technological and environmental perspectives deriving from the use of compost isolated biosurfactants in the place of synthetic surfactants.     

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.     

A chemox treatment for urea‐ and ammonium‐contaminated groundwater

In a pilot project performed at a fertilizer manufacturing facility, a one‐step chemical oxidation technique successfully treated urea‐ and ammonium‐contaminated groundwater. The oxidation reaction occurred in an 1,100‐gallon batch reactor. The contaminated inflow was buffered by the metered addition of sodium bicarbonate solution and subsequently treated with sodium hypochlorite in an 8:1 weight ratio of Cl₂:N. In an instantaneous reaction, the urea and ammo‐nium‐N were completely oxidized to nitrogen gas that was vented to the atmosphere during mixing. The pH of the reactor discharge was ?6.5. Sodium sulfite was used to reduce residual hypochlorite in the reactor effluent to chloride to provide process water with characteristics suitable for discharge. Oxidation rates were similar with different strengths of hypochlorite; however, a 5 to 6 percent sodium hypochlorite (as Cl₂) solution was the most stable. © 2005 Wiley Periodicals, Inc.     

高效石油烃降解菌的筛选及其对原油污染土壤的修复

从陕北原油污染土壤中筛选出7株高效石油烃降解菌,其中黄杆菌属CC-2、不动细菌属SC-5、假单胞菌属SC-6表现出较强的石油烃降解能力。通过单因素试验和正交试验考察总石油烃(TPH)降解效果的影响因素,得出各因素对TPH降解率影响程度的大小次序为:溶液p H降解温度降解菌接种量摇床转速,且在降解菌接种量为7%(φ)、溶液p H为7、降解温度为30℃、摇床转速为150 r/min的最适处理条件下,菌株SC-6的TPH降解率可达61.23%。原油污染土壤生物修复实验结果表明:高效石油烃降解菌的投加有利于土壤TPH降解率和酶活性的提高;"菌株SC-6+营养剂"组修复处理42 d后的TPH降解率可达57.59%。     

Remediation of uranium-contaminated soil using the segmented gate system and containerized vat leaching techniques: A cost-effectiveness study

Using an innovative, two-stage process to remediate uranium-contaminated soils, researchers at Los Alamos National Laboratory's (LANL's) Technical Area 33 (TA-33) successively reduced 218 cubic yards of contaminated soil to approximately 30 gallons of leachate solution and resins. In the first step, the contaminated soil is separated from the clean soil using the Thermo Nuclean (a division of the Thermo NUtech company) Segmented Gate System (SGS). Contaminated soil proceeds via conveyor belt to a separate storage bin to await further processing, while uncontaminated soil is returned to its original location. From the 218 cubic yards of soil excavated from the test site at TA-33, only seven cubic yards were found to contain uranium contamination above the criterion release limit, yielding an initial waste volume reduction of 97 percent. Using the containerized vat leaching (CVL) method, a technique borrowed from the mining industry, the uranium was then removed from the reduced volume of contaminated soil. This article describes the two processes and analyzes potential cost savings based on different disposal and storage options.     

Evaluation of leaching and extraction procedures for soil and waste

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.     

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.     

重金属污染土壤生物毒性的发光菌法测定及评价

向土壤中人为投加重金属污染物,制备了重金属含量不同的一系列污染土壤,对土壤重金属浸提条件进行了探究,并应用明亮发光杆菌T3（Photobacterium phosphoreum T3）对单一Cu、Cd和Pb污染及Cu-Cd和Cu-Pb复合重金属污染土壤的生物毒性进行了测定。实验结果表明,土壤重金属的最佳浸提剂为0.1 mol/L HCl溶液,最佳浸提时间为2.0 h。在单一重金属污染条件下：Cu表现出低浓度促进生长、高浓度抑制生长的双重生物效应,而Cd和Pb则表现出浓度与生物毒性的正相关性;3种重金属污染土壤的毒性强弱顺序为Cd>Pb>Cu。在复合重金属污染条件下,由于重金属之间的相互作用,污染土壤的生物毒性增强。     

铜基钯镍退镀液中铜的再生利用

采用硫氰酸盐沉铜法回收铜基钯镍退镀液中的铜。沉铜的优化工艺条件为初始Cu~(2+)质量浓度3.84 g/L、Cu~(2+)与Na SCN及Na_2SO_3摩尔比1∶4∶0.6、沉铜反应温度30℃,陈化时间24 h,沉铜反应后退镀液中Cu~(2+)残留量仅为0.025 mg/L。在此条件下加入聚乙二醇1.5 g/L,并提高分散液温度至50℃,可制得平均粒径为0.472μm的CuSCN超细粉体。CuSCN粉体为类球形,为含α、β两种晶型的混晶。     

Ex‐situ efficacy analysis of brine remediation products in clay loam soil

This study evaluated the effectiveness of gypsum and three proprietary products to remediate brine‐contaminated soil. The research objective was to determine if additives could increase plant cover germination in soils without costly prior soil‐washing or dilution techniques. The soil was shredded using a soil shredder equipped with a spray bar to apply the individual treatments of DeSalt Plus, SoilTech, Chlor*rid, and calcium sulfate (gypsum). Treatments were placed in 40‐mm high‐density polyethylene cells and small drainage systems were installed to allow removal of excess water. An initial 10‐point soil composite was taken from bulk untreated soils at a depth of more than 2.5 cm. Five‐point composite samples were collected from the same depth at weekly intervals and analyzed for: electrical conductivity, sodium adsorption ratio, cation exchange capacity, sodium, calcium, magnesium, potassium, chlorides, and pH. The Gapon selectivity coefficient was calculated and utilized to quantify the affinity for binding between ionic alkali salt constituent groups Na⁺, Ca ⁺⁺, and Mg ^++. Soil analysis indicated product‐related improvements in and bioavailability of salts. The nature of the products requires some prior treatment such as soil washing or dilution using clean soil to lower electroconductivity levels and allow the site to vegetate.     

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.     

重庆某铅污染场地稳定化修复技术研究

以重庆市某铅污染场地为研究对象,选用多种稳定化药剂对土壤开展稳定化修复技术研究,着重探讨了不同单一药剂与复配药剂对土壤铅浸出浓度的影响。实验结果表明:磷酸二氢钠(MSP)、磷酸氢二钠、磷酸钠和石灰4种无机药剂中MSP的稳定化修复效果最佳,且磷酸盐类的稳定化修复效果整体上优于石灰;MSP与少量有机药剂腐殖酸复配施用的稳定化修复效果优于单独施加MSP;在MSP投加比(与土壤的质量比)为5%、腐殖酸投加比为2%、养护时间为7 d的最优工艺条件下,土壤中铅的浸出浓度由41.70 mg/L降至0.16 mg/L,低于《生活垃圾填埋场污染控制标准》(GB 16889—2008)中规定的0.25 mg/L浓度限值。     

RECOVERY OF GALLIUM FROM COAL FLY ASH BY A DUAL REACTIVE EXTRACTION PROCESS

The extraction of gallium from coal fly ash by leaching and extraction with commercial extractants Amberlite LA-2 and LIX 54N dissolved in kerosene was studied. Leaching of gallium and other metals from the fly ash was carried out with 6 M hydrochloric acid. The leaching liquor is first contacted with Amberlite LA-2 which extracts the gallium and iron. The iron is then precipitated with sodium hydroxide, while gallium remains in solution. Gallium is extracted selectively from the base solution with LIX 54; the resulting stripped solution contains 83% of the gallium present in the leaching liquor. A flow diagram for this dual-extraction process is proposed.