Characteristics of a bioxalate chelating extraction process for removal of chromium,copper and arsenic from treated wood

The disposal of wood waste treated with chromated copper arsenate (CCA) is a problem in many countries. We have proposed a novel chelating extraction technique for CCA-treated wood using bioxalate, a solution of oxalic acid containing sufficient sodium hydroxide to adjust the pH to 3.2, which is an effective way to obtain an extraction efficiency of 90% for chromium, copper, and arsenic. The purpose of the present study was to investigate the characteristics of bioxalate extraction of CCA-treated wood. Extractions of CCA-treated western hemlock chips with solutions of bioxalate, oxalic acid, and sodium hydroxide were carried out. The use of bioxalate was confirmed as the most effective extraction technique for chromium, copper and arsenic, with an efficiency of 90%. Extraction with simple oxalic acid was ineffective for copper (less than 40% extraction efficiency), but effective for chromium and arsenic, with 90% efficiency. Sodium hydroxide showed a similar tendency, being ineffective for chromium and copper (less than 20% extraction efficiency), but relatively effective for arsenic (around 70–80% efficiency). We also discovered an interesting phenomenon whereby the addition of sodium hydroxide to a simple oxalic acid solution during the oxalic acid extraction progress resulted in dramatically increased extraction efficiency for copper, chromium and arsenic, up to 90%. Although oxalic acid was ineffective for copper extraction, the addition of sodium hydroxide during the oxalic acid extraction process rendered it effective.     

Iron and aluminium based adsorption strategies for removing arsenic from water

Arsenic is a commonly occurring toxic metal in natural systems and is the root cause of many diseases and disorders. Occurrence of arsenic contaminated water is reported from several countries all over the world. A great deal of research over recent decades has been motivated by the requirement to lower the concentration of arsenic in drinking water and the need to develop low cost techniques which can be widely applied for arsenic removal from contaminated water. This review briefly presents iron and aluminium based adsorbents for arsenic removal. Studies carried out on oxidation of arsenic(III) to arsenic(V) employing various oxidising agents to facilitate arsenic removal are briefly mentioned. Effects of competing ions, As:Fe ratios, arsenic(V) vs. arsenic(III) removal using ferrihydrite as the adsorbent have been discussed. Recent efforts made for investigating arsenic adsorption on iron hydroxides/oxyhydroxides/oxides such as granular ferric hydroxide, goethite, akaganeite, magnetite and haematite have been reviewed. The adsorption behaviours of activated alumina, gibbsite, bauxite, activated bauxite, layered double hydroxides are discussed. Point-of-use adsorptive remediation methods indicate that Sono Arsenic filter and Kanchan™ Arsenic filter are in operation at various locations of Bangladesh and Nepal. The relative merits and demerits of such filters have been discussed. Evaluation of kits used for at-site arsenic estimation by various researchers also forms a part of this review.     

活性污泥法处理含砷废水初探

文章概述了含砷废水的产生及其处理方法，重点介绍了国内外研究报道较少的活性污泥法，以引起人们对这一有效除砷方法的重视。通过总结活性污泥法除砷的研究进展，探讨了活性污泥除砷的机理和影响因素，并提出今后要从活性污泥法除砷的机理、除砷工艺、及含砷废渣处理三方面开展研究，以促进该方法的应用。     

A novel extractant for removal of hazardous metals from preservative-treated wood waste

The purpose of this study was to develop a one-step metal extraction process that would effectively remove hazardous elements from wood powder or chips of western hemlock [Tsuga heterophylla (Raf.) Sarg.] treated with chromated copper arsenate (CCA) preservative. In addition, we tested this method for wood treated with other copper-based preservatives such as ammoniacal copper quaternary (ACQ) and copper, boron, and azole (CuAz). A bioxalate solution consisting of 0.125 M oxalic acid adjusted to pH 3.2 with sodium hydroxide was tested for its ability to extract chromium, copper, and arsenic from wood treated with CCA and copper from ACQ, CuAz, or a mixture of CCA-, ACQ-, and CuAz-treated wood in single step. The extraction proceeded efficiently with 6 h of treatment, and was insensitive to the differences in chemical characteristics, including solubility of individual elements. After 6 h of treatment, approximately 90% of chromium, copper, and arsenic were effectively removed from wood treated with CCA or a mixture of CCA, ACQ, and CuAz and 90% of copper from ACQ- and CuAz-treated wood. These results demonstrate that the solvent extraction technique using pH-adjusted bioxalate solution with sodium hydroxide is a promising method for pollution minimization by various types of wastes contaminated with heavy metals and arsenic.     

Removal of Cr(VI) from Cr-contaminated groundwater through electrochemical addition of Fe(II)

The conventional chemical reduction-precipitation technique in the removal of Cr(VI) from contaminated groundwater involves a two-step process whereby Cr(VI) is first reduced to Cr(III) at an acidic pH by a reducing agent and in a subsequent step, Cr(III) is precipitated as insoluble hydroxide at an alkaline pH. In a variation of this method, Fe(II) is added electrochemically to the Cr(VI) containing water. From a pure iron electrode, Fe(2+) ions are released into the solution and bring forth the reduction of Cr(VI). At the cathode, H(2)O is reduced whereby the OH(-) ions entering the solution keep the pH of the solution in the alkaline range. This latter fact greatly facilitates simultaneous reduction of Cr(VI) to Cr(III) and co-precipitation of hydroxides of trivalent Cr and Fe. On the basis of a set of experimental data, it is shown that this process is both thermodynamically and kinetically efficient, meaning, with the electrochemical method, rapid and nearly complete removal of Cr(VI) from a groundwater source with both high and low levels of Cr-contamination can be achieved. These factors make the electrochemical process superior to the conventional chemical process in remediation of Cr-contaminated groundwater.     

Color removal from dye-containing wastewater by magnesium chloride

Color removal by MgCl(2) when treating synthetic waste containing pure dyes was studied. The color removal efficiency of MgCl(2)/Ca(OH)(2) was compared with that of Al(2)(SO(4))(3), polyaluminum chloride (PAC) and FeSO(4)/Ca(OH)(2). The mechanism of color removal by MgCl(2) was also investigated. The experimental results show that the color removal efficiency of MgCl(2) is related to the type of dye and depends on the pH of the waste and the dosage of the coagulants used. Treatment of waste containing reactive dye or dispersed dye with MgCl(2) yielded an optimum color removal ratio when the pH of the solution was equal to or above 12.0. For both the reactive and dispersed dye waste, MgCl(2)/Ca(OH)(2) was shown to be superior to MgCl(2)/NaOH, Al(2)(SO(4))(3), PAC and FeSO(4)/Ca(OH)(2) for color removal. A magnesium hydroxide precipitate formed at pH values greater than 12.0, which provided a large adsorptive surface area and a positive electrostatic surface charge, enabling it to remove the dyes through charge neutralization and an adsorptive coagulating mechanism. So, the MgCl(2)/Ca(OH)(2) system is a viable alternative to some of the more conventional forms of chemical treatment, especially for treating actual textile waste with high natural pH.     

Optimization of Fenton's oxidation of chemical laboratory wastewaters using the response surface methodology

Establishing a treatment process for practical and economic disposal of laboratory wastewaters has become an urgent environmental concern of the Department of Chemical Engineering of the Universidade Estadual de Maringá (State University of Maringá), Brazil. Fenton and related reactions are potentially useful oxidation processes for destroying toxic organic compounds in water. In these reactions, hydrogen peroxide is combined with ferrous or ferric iron in the presence or absence of light to generate hydroxyl radicals (.OH). The feasibility of Fenton's reagent to treat waste chemicals from an academic research laboratory was investigated in this study. A response surface methodology was applied to optimize the Fenton oxidation process conditions using chemical oxygen demand (COD) removal as the target parameter to optimize, and the reagent concentrations, as related to the initial concentration of organic matter in the effluent, and pH as the control factors to be optimized. Maximal COD removal (92.3%) was achieved when wastewater samples were treated at pH 4 in the presence of hydrogen peroxide and iron in the ratios [COD]:[H2O2]=1:9 and [H2O2]:[Fe2+]=4.5:1. Under these conditions, it was possible to obtain simultaneously maximal COD removal and minimal chemical sludge after treatment, which is a residue that needs further processing.     

Betaine removal during thermo- and mesophilic aerobic batch biodegradation of beet molasses vinasse: influence of temperature and pH on the progress and efficiency of the process

The key issue in achieving a high extent of biodegradation of beet molasses vinasse is to establish the conditions for the assimilation of betaine, which is the main pollutant in this high-strength industrial effluent. In the present study, aerobic batch biodegradation was conducted over the temperature range of 27-63°C (step 9°C), at a pH of 6.5 and 8.0, using a mixed culture of bacteria of the genus Bacillus. Betaine was assimilated at 27-54°C and the pH of 8.0, as well as at 27-45°C and the pH of 6.5. The processes where betaine was assimilated produced a high BOD(5) removal, which exceeded 99.40% over the temperature range of 27-45°C at the pH of 8.0, as well as at 27°C and the pH of 6.5. Maximal COD removal (88.73%) was attained at 36°C and the pH of 6.5. The results indicate that the process can be applied on an industrial scale as the first step in the treatment of beet molasses vinasse.     

Bioremediation of Acidic and Metalliferous Drainage (AMD) through organic carbon amendment by municipal sewage and green waste

Pit lakes (abandoned flooded mine pits) represent a potentially valuable water resource in hot arid regions. However, pit lake water is often characterised by low pH with high dissolved metal concentrations resulting from Acidic and Metalliferous Drainage (AMD). Addition of organic matter to pit lakes to enhance microbial sulphate reduction is a potential cost effective remediation strategy. However, cost and availability of suitable organic substrates are often limiting. Nevertheless, large quantities of sewage and green waste (organic garden waste) are often available at mine sites from nearby service towns. We treated AMD pit lake water (pH 2.4) from tropical, North Queensland, Australia, with primary-treated sewage sludge, green waste, and a mixture of sewage and green waste (1:1) in a controlled microcosm experiment (4.5 L). Treatments were assessed at two different rates of organic loading of 16:1 and 32:1 pit water:organic matter by mass. Combined green waste and sewage treatment was the optimal treatment with water pH increased to 5.5 in only 145 days with decreases of dissolved metal concentrations. Results indicated that green waste was a key component in the pH increase and concomitant heavy metal removal. Water quality remediation was primarily due to microbially-mediated sulphate reduction. The net result of this process was removal of sulphate and metal solutes to sediment mainly as monosulfides. During the treatment process NH(3) and H(2)S gases were produced, albeit at below concentrations of concern. Total coliforms were abundant in all green waste-treatments, however, faecal coliforms were absent from all treatments. This study demonstrates addition of low-grade organic materials has promise for bioremediation of acidic waters and warrants further experimental investigation into feasibility at higher scales of application such as pit lakes.     

不同操作条件对纳滤膜去除水中五价砷的研究

采用纳滤膜（NF90）过滤自配含砷水,研究在不同操作条件下纳滤膜对水中砷去除效果的影响。本实验探讨膜进水浓度、水的pH值、膜进水温度、操作压力、水中天然有机物浓度等对膜除砷效率的影响。结果表明：纳滤膜对水中五价砷（As（Ⅴ））的去除率很高,最高去除率能达到99%,在实验的前2.5个小时内,砷的去除率均在90%以上。但是,纳滤膜除砷效率随着时间变化,去除率会降低。不同的操作条件对纳滤膜除砷的影响很大,研究不同条件的影响对应用很有意义。     

MAP法与沸石吸附组合工艺的脱氮除磷实验研究

以高浓度氮磷模拟废水为处理对象,通过静态实验研究了MAP法（磷酸铵镁法）与沸石吸附组合工艺的脱氮除磷效果。以MAP法除磷脱氮后的出水作为沸石吸附过程的进水,最终出水的氮、磷去除率可达86．69％和99．9％,且在MAP反应过程中采取较高的pH值和Mg^2＋浓度有利于后期沸石对氮、磷的吸附去除。     

Biosorption of copper (II) from chemical mechanical planarization wastewaters

Copper Chemical Mechanical Planarization (Cu-CMP) is a critical step in integrated circuit (IC) device manufacturing. CMP and post-CMP cleaning processes are projected to account for 30-40% of the water consumed by IC manufacturers in 2003. CMP wastewater is expected to contain increasing amounts of copper as the industry switches from Al-CMP to Cu-CMP causing some IC manufacturers to run the risk of violating discharge regulations. There are a variety of treatment schemes currently available for the removal of heavy metals from CMP wastewater, however, many introduce additional chemicals to the wastewater, have large space requirements, or are expensive. This work explores the use of microorganisms for waste treatment. A Staphylococcus sp. of bacteria was isolated and studied to determine the feasibility for use in removing copper from Cu-CMP wastewater. A model Cu-CMP wastewater was developed and tested, as well as actual Cu-CMP wastes. Continuous-flow packed column experiments were performed to obtain adsorption data and show copper recovery from the waste. A predictive, empirical model was used to accurately describe Cu removal. Additionally, the immobilized cells were regenerated, allowing for the concentration and potential recovery of copper from the wastewater.     

再生造纸废水絮凝除浊试验研究

本研究采用絮凝法对再生造纸废水中含细小纤维、无机填料的悬浮物进行处理试验，比较了硫酸亚铁与聚丙烯酰胺复合絮凝剂和聚硅酸氯化铁盐两种絮凝剂的絮凝效果，研究了制备聚硅酸氯化铁盐的铁硅比、pH值、碱化度以及投加量与废水除浊率之间的相互关系。实验结果表明：在最佳条件下，絮凝效果优异，除浊率达到98％，上清液无色透明。     

Potential anthropogenic mobilisation of mercury and arsenic from soils on mineralised rocks, Northland, New Zealand

Eroded roots of hot spring systems in Northland, New Zealand consist of mineralised rocks containing sulfide minerals. Marcasite and cinnabar are the dominant sulfides with subordinate pyrite. Deep weathering and leached soil formation has occurred in a warm temperate to subtropical climate with up to 3 m/year rainfall. Decomposition of the iron sulfides in natural and anthropogenic rock exposures yields acid rock drainage with pH typically between 2 and 4, and locally down to pH 1. Soils and weathered rocks developed on basement greywacke have negligible acid neutralisation capacity. Natural rainforest soils have pH between 4 and 5 on unmineralised greywacke, and pH is as low as 3.5 in soils on mineralised rocks. Roads with aggregate made from mineralised rocks have pH near 3, and quarries from which the rock was extracted can have pH down to 1. Mineralised rocks are enriched in arsenic and mercury, both of which are environmentally available as solid solution impurities in iron sulfides and phosphate minerals. Base metals (Cu, Pb, Zn) are present at low levels in soils, at or below typical basement rock background. Decomposition of the iron sulfides releases the solid solution arsenic and mercury into the acid rock drainage solutions. Phosphate minerals release their impurities only under strongly acid conditions (pH<1). Arsenic and mercury are adsorbed on to iron oxyhydroxides in soils, concentrated in the C horizon, with up to 4000 ppm arsenic and 100 ppm mercury. Waters emanating from acid rock drainage areas have arsenic and mercury below drinking water limits. Leaching experiments and theoretical predictions indicate that both arsenic and mercury are least mobile in acid soils, at pH of c. 3-4. This optimum pH range for fixation of arsenic and mercury on iron oxyhydroxides in soils is similar to natural pH at the field site of this study. However, neutralisation of acid soils developed on mineralised rocks is likely to decrease adsorption and enhance mobility of arsenic and mercury. Hence, development of farmland by clearing forest and adding agricultural lime may mobilise arsenic and mercury from underlying soils on mineralised rocks. In addition, arsenic and mercury release into runoff water will be enhanced where sediment is washed off mineralised road aggregate (pH 3) on to farm land (pH>6). The naturally acid forest soils, or even lower pH of natural acid rock drainage, are the most desirable environmental conditions to restrict dissolution of arsenic and mercury from soils. This approach is only valid where mineralised soils have low base metal concentrations.     

绿色修井技术的研究与应用

为了避免在修井过程中产生的落地油、油砂、油水混合液和洗井液等对环境造成污染,辽河石油勘探局经过多年的研究与实践已研究出一整套完备的绿色环保修井技术,包括抽油杆刮油、油管泄油、密闭连续冲砂、软捞砂、快速防喷、汽化水回收等修井技术,在施工全过程中采取了预防污染的措施,将生产技术、生产过程、经营管理及产品质量与物流、能量、信息管理等有机结合起来,并优化运行方式,从而实现了最小的环境影响、最少的资源消耗、最佳的管理模式以及最优化的经济水平。并取得多项专利成果。     

Low-energy sodium hydroxide recovery for CO2 capture from atmospheric air—Thermodynamic analysis

To reduce the risks of climate change, atmospheric concentrations of greenhouse gases must be lowered. Direct capture of CO₂ from ambient air, “air capture”, might be one of the few methods capable of systematically managing dispersed emissions. The most commonly proposed method for air capture is a wet scrubbing technique which absorbs CO₂ in an alkaline absorbent, i.e. sodium hydroxide producing an aqueous solution of sodium hydroxide and sodium carbonate. In most of the previous works it was assumed that the absorbent would be regenerated and CO₂ liberated from the alkaline carbonate solution using a lime and calcium carbonate causticization cycle.We describe a novel technique for recovering sodium hydroxide from an aqueous alkaline solution of sodium carbonate and present an end-to-end energy and exergy analysis. In the first step of the recovery process, anhydrous sodium carbonate is separated from the concentrated sodium hydroxide solution using a two-step precipitation and crystallization process. The anhydrous sodium carbonate is then causticized using sodium tri-titanate. The titanate direct causticization process has been of interest for the pulp and paper industry and has been tested at lab- and pilot-scale. In the causticization process, sodium hydroxide is regenerated and carbon dioxide is liberated as a pure stream, which is compressed for use or disposal. The technique requires ～50% less high-grade heat than conventional causticization and the maximum temperature required is reduced by at least 50 °C. This titanate cycle may allow a substantial reduction in the overall cost of direct air capture.     

Heavy metal removal and cyanide destruction in the metal plating industry: an integrated approach from egypt

Wastewater produced from a metal plating is a major environmental problem. Industrial auditing revealed that the main source of pollution mainly originated from rinsing water. The characterization of final effluent showed that it is highly contaminated with hazardous heavy metals and cyanide. The concentration of copper, hexavalent chromium, nickel, and cyanide in the rinsing water of metal plating department was 14.8, 40.9, 13.3, and 19 mg/l, respectively. The concentration of cyanide and zinc from the galvanizing department reached 60 and 80 mg/l. The remediation scheme included the application of in-plant control measures via changing the rinsing process followed by the destruction of cyanide and reduction of hexavalent chromium bearing wastes. The pretreated wastes were then mixed with other industrial wastes prior to a combined chemical coagulation-sedimentation using lime and/or lime in combination with ferric chloride. The results indicated that, after applying the waste minimization measures alone at the source, prior to final treatment of industrial waste, removal rates of cyanide, copper, nickel, and chromium concentrations were 23.2%, 14.9%, 32.3%, and 55.3%, respectively in the rinse water from metal plating department. Furthermore, the removal rates of cyanide and zinc in the galvanizing department reached 59.7% and 24.3. The integrated control measures and treatment scheme led to more than 99% removal of copper, nickel, chromium, and zinc, while the complete removal of cyanide was achieved in the final effluent.     

Fluoride removal by a continuous flow electrocoagulation reactor

Long-term consumption of water containing excessive fluoride can lead to fluorosis of the teeth and bones. Electrocoagulation (EC) is an electrochemical technique, in which a variety of unwanted dissolved particles and suspended matter can be effectively removed from an aqueous solution by electrolysis. Continuous flow experiments with monopolar aluminium electrodes for fluoride removal were undertaken to investigate the effects of the different parameters such as: current density (12.5-50A/m(2)), flow rate (150-400 mL/min), initial pH (4-8), and initial fluoride concentration (5-25mg/L). The highest treatment efficiency was obtained for the largest current and the removal efficiency was found to be dependent on the current density, the flow rate and the initial fluoride concentration when the final pH ranged between 6 and 8. The composition of the sludge produced was analysed using the X-ray diffraction (XRD) spectrum. The strong presence of the aluminium hydroxide [Al(OH)(3)] in the above pH range, which maximizes the formation of aluminium fluoride hydroxide complex [Al(n)F(m)(OH)(3n-m)], is the main reason for defluoridation by electrocoagulation. The results obtained showed that the continuous flow electrocoagulation technology is an effective process for defluoridation of potable water supplies and could also be utilized for the defluoridation of industrial wastewater.     

Utilization of UV‐A and UV‐C radiation in advanced oxidation processes with the intention of removing color and organic matter from the gross leachate of a stabilized sanitary landfill

The present work investigated color and biochemical oxygen demand (COD) removal from treated landfill leachate via advanced oxidative processes (AOPs) artificially emitted. The AOP H₂O₂/UV, TiO₂/UV, and photolysis were tested in two bench‐scale photoreactors: The first one with UV‐C lamp and the other with UV‐A lamp associated or not with coagulation / flocculation pretreatment. Crude leachate samples with pH ranging from 8 to 3 were used, and time varied in 30, 45, and 60 minutes. Experiments were performed in two stages: step 1 with a 20 mL volume from each sample and step 2 with repetition of the best results from the previous step, adopting the 150 mL volume. In step 1, the AOP applied in the crude leachate sample showed the best results, standing out H₂O₂/UV‐C with 30 minutes and TiO₂/UV‐A with 60 minutes. In step 2, H₂O₂/UV‐C had a 60% color removal and 25% COD reduction, while TiO₂/UV‐A had a 10% color removal and 20% COD reduction. Therefore, the H₂O₂/UV‐C process was the most efficient, because the complex characteristics of the effluent interfered in the TiO₂/UV‐A efficiency, but it is necessary to eliminate the process interferences. The use of artificial radiation is a viable alternative; however, it can be costly, being relevant in the associations between processes with artificial UV and solar UV, as the natural radiation becomes more attractive and allows the process operating costs reduction.     

Preservative leaching from weathered CCA-treated wood

Disposal of discarded chromated copper arsenate (CCA)-treated wood in landfills raises concerns with respect to leaching of preservative compounds. When unweathered CCA-treated wood is leached using the toxicity characteristic leaching procedure (TCLP), arsenic concentrations exceed the toxicity characteristic (TC) limit of 5mg/L in most cases. The majority of discarded CCA-treated wood, however, results from demolition activities, where the wood has typically been subjected to weathering. Since preservatives do migrate from the wood during its normal use, leaching characteristics of weathered and aged CCA-treated wood may differ from unweathered wood. To evaluate this, CCA-treated wood removed from service after various degrees of weathering was collected from multiple sources and leached with the TCLP, the synthetic precipitation leaching procedure (SPLP) and California's waste extraction test (WET). Five to seven individual pieces of wood were analyzed from each source. The average TCLP arsenic concentration for the 14 sources ranged from 3.2 to 13 mg/L. The average TCLP concentrations of the 100 wood pieces tested were 6.4, 5.9 and 3.2 mg/L for arsenic, copper and chromium, respectively. Overall, in 60 out of 100 samples tested by the TCLP, arsenic concentrations exceeded 5 mg/L (the TC regulatory value). SPLP leachate concentrations were similar to TCLP concentrations, although copper leached somewhat more with the TCLP. WET leachate concentrations were approximately a factor of 10 higher than TCLP concentrations. Discarded CCA-treated wood, even after exposure to years of weathering, often exceeds the TC limit for arsenic and without the current regulatory exemption would possibly require management as a TC hazardous waste in the US.