Study on Optimal Conditions for Recovery of EDTA from Soil Washing Effluents

The recovery of ethylenediaminetetraacetic acid (EDTA) from washing effluents is essential to reduce the cost of EDTA-enhanced soil washing and the production of wastewater. This study evaluated a recovery method, in which Pb or Zn was first dissociated from Pb– or Zn–EDTA complex through the replacement reaction by adding FeCl3 and then removed as phosphate precipitates through adding Na2HPO4. Finally, Fe(III) was removed as Fe(OH)3 precipitates through adding Ca(OH)2. As a result, EDTA was recovered as Ca–EDTA for further use in soil washing process. The optimal conditions for EDTA recovery, including the molar ratios of FeCl3 and Na2HPO4 to EDTA as well as the pH after adding Na2HPO4 and adding Ca(OH)2, were well investigated. Under the optimal conditions, 96% of Pb or 83% of Zn was removed from the Pb– or Zn–EDTA, respectively. The four-cycle recovery and reuse of EDTA experiments indicated the recovered EDTA from soil washing effluents did not lose much chelating capacity for Pb removal. However, there is a loss of 15% of its chelating capacity in the first cycle reuse for Zn-contaminated soil washing due to substantial Zn residual in the recovered EDTA solution.     

Complicating Factors of Using Ethylenediamine Tetraacetic Acid to Enhance Electrokinetic Remediation of Multiple Heavy Metals in Clayey Soils

Batch and electrokinetic experiments were conducted to investigate the removal of three different heavy metals, chromium(VI), nickel(II), and cadmium(II), from a clayey soil by using ethylenediamine tetraacetic acid (EDTA) as a complexing agent. The batch experiments revealed that high removal of these heavy metals (62–100%) was possible by using either a 0.1?M or 0.2?M EDTA concentration over a wide range of pH conditions (2–10). However, the results of the electrokinetic experiments using EDTA at the cathode showed low heavy metal removal efficiency. Using EDTA at the cathode along with the pH control at the anode with NaOH increased the pH throughout the soil and achieved high (95%) Cr(VI) removal, but the removal of Ni(II) and Cd(II) was limited due to the precipitation of these metals near the cathode. Apparently, the low mobility of EDTA and its migration direction, which opposed electroosmotic flow, prevented EDTA complexation from occurring. Overall, this study found that many complicating factors affect EDTA-enhanced electrokinetic remediation, and further research is necessary to optimize this process to achieve high contaminant removal efficiency.     

EDTA-Enhanced Washing for Remediation of Pb- and/or Zn-Contaminated Soils

The effects of the operating conditions, the initial concentrations of heavy metals in soils, and the competition among heavy metals during ethylenediaminetetraacetic acid (EDTA)-enhanced soil washing were extensively investigated using batch experiments with Pb- and/or Zn-contaminated soils aiming to determine the heavy-metal removal for different types of contaminations and to optimize the process parameters. Pb or Zn removal efficiency was found to be dependent on contact time, pH, concentrations of EDTA, and their initial concentrations in contaminated soils. The experimental results showed that the heavy-metal removal efficiency increased with a higher initial concentration of heavy metals in soils, and the concentrations of heavy metals in the solutions after washing were linearly correlated with their initial concentrations in soils. The study of the competition among heavy metals indicated that when EDTA was present in solution with the concentration less than the stoichiometric requirements, Pb removal efficiency was higher than that of Zn; on the other hand, when EDTA concentration was greater, Pb and Zn removal efficiencies were almost the same.     

Chemical-Enhanced Washing for Remediation of Soils Contaminated with Marine Diesel Fuel in the Presence/Absence of Pb

The effects of the operating conditions, the initial concentrations of marine diesel fuel (MDF) and the coexisting Pb in the soil, and the ethylene diamine tetra acetic salt (EDTA) in solution on MDF removal by sodium dodecyl sulfate (SDS) washing were extensively investigated with the aim of optimizing the process parameters and determining the MDF removal efficiency by SDS under different contamination conditions. The experimental results from batch tests indicated that the majority of MDF was removed by SDS in the first 2?h, and its optimal pH was nearly neutral. Increasing the SDS concentration linearly increased the MDF removal efficiency. At a given SDS concentration, the removal efficiency was dependent on the existing forms of MDF in soils, and the free phase of MDF was found to be more easily removed than the adsorbed phase. MDF removal by SDS was significantly reduced by the coexisting Pb in soils, which likely forms a complexation with SDS and thereby enhances the partitioning of MDF in the soil by the re-adsorption of released MDF onto the hydrophobic tails of the adsorbed SDS. EDTA alone, or with SDS, could remove MDF, but the remaining MDF in the contaminated soil after EDTA washing became more difficult to be removed by SDS. Therefore, the EDTA washing followed by SDS washing is not recommended for MDF removal.     

Enhanced Electrokinetic Remediation of Heavy Metals in Glacial Till Soils Using Different Electrolyte Solutions

Previous electrokinetic remediation studies involving the geochemical characterization of heavy metals in high acid buffering soils, such as glacial till soil, revealed significant hexavalent chromium migration towards the anode. The migration of cationic contaminants, such as nickel and cadmium, towards the cathode was insignificant due to their precipitation under the high pH conditions that result when the soil has a high acid buffering capacity. Therefore the present laboratory study was undertaken to investigate the performance of different electrolyte (or purging) solutions, which were introduced to either dissolve the metal precipitates and/or form soluble metal complexes. Tests were conducted on a glacial till soil that was spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1,000, 500, and 250 mg/kg, respectively, under the application of a 1.0 VDC/cm voltage gradient. The electrolyte solutions tested were 0.1M EDTA (ethylenediaminetetraacetic acid), 1.0M acetic acid, 1.0M citric acid, 0.1M NaCl/0.1M EDTA, and 0.05M sulfuric acid/0.5M sulfuric acid. The results showed that 46–82% of the Cr(VI) was removed from the soil, depending on the purging solution used. The highest removal of Ni(II) and Cd(II) was 48 and 26%, respectively, and this removal was achieved using 1.0M acetic acid. Although cationic contaminant removal was low, the use of 0.1M NaCl as an anode purging solution and 0.1M EDTA as a cathode purging solution resulted in significant contaminant migration towards the soil regions adjacent to the electrodes. Compared to low buffering capacity soils, such as kaolin, the removal of heavy metals from the glacial till soil was low, and this was attributed to the more complex composition of glacial till. Overall, this study showed that the selection of the purging solutions for the enhanced removal of heavy metals from soils should be primarily based upon the contaminant characteristics and the soil composition.     

As(III), As(V), Hg, and Pb Removal by Fe-Oxide Impregnated Activated Carbon

The removal of As(III), As(V), Hg(II), and Pb(II) by virgin and Fe(III) impregnated activated carbons (FeAC) was investigated. Iron-oxide impregnation increased the pHzpc of the carbon from 7.5 to about 8.2–8.7 but did not alter the surface area or the pore volume. The amount of acid or base needed to reach a given pH increased following impregnation, indicating that the FeAC was more active than its non-impregnated counterpart. Metal removal was a function of pH with removal increasing with pH for Hg(II) and Pb(II) and decreasing with pH for As(V). As(III) removal was not a strong function of pH below pH = 5, increased to a maximum at pH ≈ 7, then decreased with increasing pH. As(III) and As(V) removals were about one and two orders of magnitude higher, respectively, for the FeAC compared with the non-impregnated carbon, while Hg(II) and Pb(II) removals were only slightly higher. Fe-impregnation appears to be most effective for the anionic contaminants.     

Ex-Situ Remediation of a Metal-Contaminated Superfund Soil Using Selective Extractants

The Superfund Amendments and Reauthorization Act requires the use of remedial technologies that permanently and significantly reduce the volume, toxicity, or mobility of contaminated materials at affected sites. Extractive processes can accomplish the requirements of the Superfund Amendments and Reauthorization Act. Ethylenediaminetetraacetic acid (EDTA), N-2(acetamido)iminodiacetic acid (ADA), pyridine-2,6-dicarboxylic acid (PDA), and hydrochloric acid (HCl) were evaluated over a range of concentrations and reaction times in batch studies for their ability to remove lead (Pb) and cadmium (Cd) from a Superfund soil (Pbtotal= 65,200 mg∕kg, Cdtotal= 52 mg∕kg). Lead extraction was limited by a slow overall reaction. The order of Pb removal by extractant was EDTA > ADA > PDA > HCL. The soil was subjected to three repeated 1 h extractions in which a maximum of 86, 84, 70, and 54% of the total soil Pb was removed with EDTA, ADA, PDA, and HCl, respectively. The soil was not treated to below the Pb regulatory limit (1,000 mg∕kg), even after five extractions with 0.075 M EDTA; however, the remaining Pb occurred in a residual form. All extractants treated the soil below the proposed Cd regulatory limit (40 mg∕kg) within 1 h. With three repeated extractions EDTA, ADA, PDA, and HCl removed a maximum of 96, 100, 98, and 100% Cd, respectively. Lead recovery from spent solution was accomplished by hydroxide precipitation in the presence of excess calcium. Recovery at pH 11 was 70, 98, and 97% from the EDTA, ADA, and PDA complexes, respectively. The results indicate that the remediation of weathered, heavily Pb- and Cd-contaminated soils via extractive processes is possible under the appropriate conditions.     

Citric Acid Enhanced Remediation of Soils Contaminated with Uranium by Soil Flushing and Soil Washing

Laboratory bench-scale soil washing (batch) and flushing (column flow) experiments were conducted to determine the efficiency of citric acid as an agent to extract uranium from a synthetically contaminated sandy soil. The results of soil washing and flushing experiments indicate that citric acid is highly effective in removing uranium, and that the extraction efficiency increases with increasing citric acid concentration, especially under slightly acidic to alkaline conditions in systems containing sand coated with secondary minerals (e.g., Fe). The enhanced U(VI) desorption in the presence of citrate may be explained through several processes, including the complexation of U(VI) with citrate and extraction of secondary coatings (e.g., Fe), which results in the liberation of Fe-citrate complexes into solution. In batch washing systems, the presence of 10?3?M citric acid enhances the extraction of uranium 2.8 times greater than water alone for the conditions of the experiment. A comparison of soil washing and flushing shows that the extraction efficiency is higher in bench-scale washing experiments. A removal efficiency of up to 98% was achieved with 10 mL of 10?3?M citric acid in batch systems, whereas it required 4 pore volumes (150 mL) of 0.1 M citric acid to accomplish similar extraction efficiencies in column soil flushing systems.     

Integrated System for Remediation of Contaminated Soils

A pilot-scale study was conducted to evaluate an integrated system for the remediation of soils contaminated primarily with pentachlorophenol (PCP), a wood preserver. The integrated soil remediation system consisted of three unit processes: (1) Soil solvent washing; (2) solvent recovery; and (3) biotreatment of the contaminant residual. Pilot-scale countercurrent solvent washing was carried out using a 95% ethanol solution—a solvent that in an earlier bench-scale study was found to be effective in removing PCP and hydrocarbons (HCs) from soils. Three-stage countercurrent solvent washing of a field-contaminated soil was performed using batches of 7.5 kg of soil and 30 L of solvent (1 kg:4 L soil-to-solvent contact ratio). The washed soil was rinsed with water in a single stage after three countercurrent wash stages. Pilot-scale, three-stage countercurrent solvent washing with 95% ethanol reduced the PCP and HC contamination on the soil by 98 and 95%, respectively. The spent solvent and the spent rinse water were combined as the spent wash fluid for further treatment. A pilot-scale distillation unit was used to recover the ethanol from the spent wash fluid. The HC constituents of the spent wash fluid were removed by pH adjustment prior to feeding the spent wash fluid to a distillation unit. Greater than 96% of the ethanol in the spent wash fluid was recovered in the distillate stream, whereas PCP was captured in the bottoms stream. The bottoms stream was treated sequentially in anaerobic and aerobic granular-activated carbon fluidized-bed reactors. Complete mineralization of PCP was achieved using this treatment train.     

EDTA, NTA, Alkylphenol Ethoxylate and DOC Attenuation during Soil Aquifer Treatment

Removals of dissolved organic carbon (DOC), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and carboxylated alkylphenol polyethoxylate metabolites (APECs) were studied at the Sweetwater (Tucson, Ariz.) soil aquifer treatment site that treated chlorinated secondary effluent. The site was operated in a first phase by flooding irregularly for weeks interrupted by days of drying and in a second phase by a regular schedule of flooding for 3 days and drying for 4 days. The average hydraulic loading rates were 0.13 and 0.17?m/day in the first and second phases, respectively. During drying, oxygen intruded at least 3?m deep into the unsaturated subsurface causing nitrification of the ammonium that was retained in the top layer during flooding. Nitrification increased nitrate concentrations to >200?mg/L but most was removed to <10?mg/L during transport to 38?m depth. At 38?m depth, removals of DOC, EDTA, NTA, and APECs during the first phase were 85, 80, 90, and 98%, slightly higher (<7%) than during the second phase. Most of the DOC removal occurred during transport to 3?m and most of the trace organics removal occurred during transport from 3 to 38?m depth.     

Degradation and Mineralization of Simazine in Aqueous Solution by Ozone/Hydrogen Peroxide Advanced Oxidation

Advanced oxidation of simazine in aqueous solution by the peroxone (hydrogen peroxide/ozone) treatment was investigated using Box-Behnken statistical experiment design and response surface methodology. Effects of pH, simazine and H2O2 concentrations on percent simazine and total organic carbon (TOC) removals were investigated. Ozone concentration was kept constant at 45?mg?L?1. The optimum conditions yielding the highest simazine and TOC removals were also determined. Both simazine and peroxide doses affected simazine removal while pH and pesticide dose had more pronounced effect on mineralization (TOC removal) of simazine. Nearly 95% removal of simazine was achieved within 5 min for simazine and peroxide concentrations of 2.0 and 75?mg?L?1, respectively at pH = 7. However, mineralization of simazine was not completed even after 60 min at simazine doses above 2?mg?L?1 indicating formation of some intermediate compounds. The optimum H2O2/pH/Simazine ratio resulting in maximum pesticide (94%) and TOC removal (82%) was found to be 75/11/0.5(mg?L?1).     

Precipitative Removal of As, Ba, B, Cr, Sr, and V Using Sodium Carbonate

Sodium carbonate softening at pH 10.3 is a viable method of removing the inorganic contaminants arsenic, barium, chromium, strontium, and vanadium from drinking water sources. A broad survey revealed that removals varied widely and were dependent on solution composition. Median removals of As, Ba, Cr, Sr, and V were 24, 100, 92, 99, and 60%, respectively. Linear and nonlinear empirical models were fit for crudely estimating the removal of these contaminants in the presence of other elements that are typically removed in the softening process (i.e., calcium, magnesium, silicon, iron, and aluminum). Boron was removed to a much lesser extent (median removal 2%) indicating soda ash softening is not a promising treatment option for this purpose.     

含锰反萃液制备高纯碳酸锰工艺研究

以含锰反萃液为原料,经针铁矿法除铁、硫化除重金属、碳化、洗涤制备了合格高纯碳酸锰。考察了终点pH、反应温度对除铁率的影响和(NH4)2S加入量、温度、反应时间对重金属去除率的影响,结果表明:在pH=4.0、反应温度95℃的条件下可将铁除至1.5 mg/L以下;除铁滤液加入2.2倍计量比的(NH4)2S,在反应温度35℃、反应时间60 min的条件下,Ni、Co、Zn可降低至1 mg/L以下;除重金属滤液加入碳酸氢铵调节pH在7.0~7.2,过滤、洗涤,获得满足HG/T 2836—2011(Ⅰ型)产品标准的合格高纯碳酸锰,锰回收率为93.9%。     

Staged Coagulation for Treatment of Refractory Organics

Seasonal periods of high rainfall have been shown to cause elevated natural organic matter (NOM) loadings at treatment works. These high levels lead to difficulties in removing sufficient NOM to meet trihalomethane standards, and hence better alternative treatments are required. Here the removal of NOM was investigated by conventional coagulation treatment using both bulk and fractionated NOM. Initial experiments showed that over 70% removal of the hydrophobic and hydrophilic acid fractions was achieved at the works, while only 16% of the hydrophilic nonacid fraction was being removed. Bench scale jar testing of the isolated NOM fractions demonstrated that high removals of the hydrophobic fractions were achieved and that optimized conditions increased removal of the hydrophilic fractions, indicating that staged coagulation could be of benefit in the removal of the recalcitrant fractions. Experiments using optimized staged coagulation indicated that a small increase in the removal of the total NOM of this water was possible when compared to conventional treatment.     

Evaluation and Optimization of Bioretention Media for Treatment of Urban Storm Water Runoff

Bioretention is a relatively new urban storm water best management practice. The objective of this study is to provide insight on media characteristics that control bioretention water management behavior. Eighteen bioretention columns and six existing bioretention facilities were evaluated employing synthetic runoff. In columns, the runoff infiltration rate through different media mixtures ranged from 0.28 to 8.15?cm/min at a fixed 15 cm head. For pollutant removals, the results showed excellent removal for oil/grease (>96%). Total lead removal (from 66 to >98%) decreased when the total suspended solids level in the effluent increased (removed from 29 to >96%). The removal efficiency of total phosphorus ranged widely (4–99%), apparently due to preferential flow patterns, and both nitrate and ammonium were moderate to poorly removed, with removals ranging from 1 to 43% and from 2 to 49%, respectively. Two more on-site experiments were conducted during a rainfall event to compare with laboratory investigation. For bioretention design, two media design profiles are proposed; >96%?TSS, >96%?O/G, >98%?lead, >70%?TP, >9%?nitrate, and >20%?ammonium removals are expected with these designs     

Performance Enhancement of SBR Applying Real-Time Control

This paper presents the applications of a real-time oxidation reduction potential (ORP) and pH control system to enhance the system performance of a continuous-inflow sequencing batch reactor (SBR). The real-time controlled SBR showed better performances than sequential control regarding substrate removal efficiency and cost reduction. In substrate removal efficiency, good COD, total Kjeldahl nitrogen, and NH+4 removals were achieved by real-time and conventional sequential controlled systems. However, the poor removal of total nitrogen caused by incomplete denitrification in the sequential controlled SBR was improved significantly to 91% by real-time control. Moreover, in contrast with sequential controlled SBR, the real-time controlled SBR can save 14–32% of aeration energy and 11–29% of reactor capacity. Observation of nitrogen compound variations showed nitrites accumulated during the aerobic phase of the real-time controlled SBR. In addition, the kinetics of nitrification and denitrification also proved that the real-time controlled SBR performed the nitrite-type nitrification, which was identified as the key-point of system performance enhancement in the real-time controlled SBR.     

上海苏州河底泥重金属淋洗效果的研究

采用批提取实验n）atchexperiment）,利用柠檬酸溶液、酒石酸溶液、聚天冬氨酸溶液及EDTA溶液依次淋洗受重金属污染的苏州河底泥。分析不同溶液在不同浓度下其淋洗液中的重金属含量及其浸提率,优化重金属淋洗试剂及其相应的浓度。结果表明,柠檬酸溶液、酒石酸溶液和EDTA溶液对底泥重金属均有显著的淋滤效果．其中．柠檬酸溶液的淋洗效果最好,其浓度为0．75mol／L时,对不同重金属的浸提率均在90％以上。聚天冬氨酸溶液对重金属的浸提能力相对较差,对底泥中的Cu淋洗能力较强,但浸提率亦不足60％。聚天冬氨酸对碳酸盐态重金属有较好的淋洗效果．酒石酸淋洗可去除交换态、碳酸盐结合态和氧化物结合态的重金属。     

Enhanced Soil Flushing for Simultaneous Removal of PAHs and Heavy Metals from Industrial Contaminated Soil

Polycyclic aromatic hydrocarbons (PAHs) and heavy metals are environmental concerns and must be removed to acceptable levels. This paper evaluates different flushing agents to enhance the remediation of soil contaminated with PAHs and heavy metals at a former manufactured gas plant site. Four flushing column tests at a constant hydraulic gradient of 1.2 were conducted using four different flushing agents, which included deionized water, chelant (0.2?M EDTA), surfactant (5% Igepal CA-720), and cyclodextrin (10% hydroxypropyl-β-cyclodextrin or HPCD). Additional column tests using Igepal and HPCD at a lower hydraulic gradient of 0.2 were conducted to investigate the effects of rate-limited desorption or solubilization of PAHs. The results showed that the EDTA produced the maximum metal removal from the soil compared with deionized water, Igepal, and HPCD under different hydraulic gradient conditions. The 0.2?M EDTA flushing solution removed approximately 25–75% of the toxic heavy metals found in the soil. None of the PAHs were removed from the soil when deionized water and EDTA were the flushing solutions. The PAHs removal efficiencies in the Igepal and HPCD systems decreased as the hydraulic gradient decreased. However, the surfactant-enhanced systems were more efficient in removing PAHs from the soil than the HPCD systems under high- and low-hydraulic gradients. The results also demonstrated that the removal of PAHs in surfactant-enhanced systems depended upon the micelles formation, whereas in the HPCD-enhanced systems, it depended upon the sterioselective diffusion of the PAHs to the nonpolar cavity of the HPCD. Overall, this study showed that the contaminant removal in soil flushing systems depends on the flushing solution affinity and selectivity toward the target contaminant and the existing hydraulic gradient condition.     

EDTA滴定法测定锡铅焊料中高含量镉

实验对已报道的EDTA络合滴定法测定锡铅焊料中高含量镉的方法进行了改进,通过将称样量增至1.50g和用六次甲基四胺缓冲溶液(pH=6.00±0.02)来替代乙酸-乙酸钠缓冲溶液的方法改善了EDTA络合滴定法测定锡铅焊料中镉的精密度,同时采用铅标准溶液代替镉标准溶液标定EDTA标准滴定溶液,避免了标定时指示剂出现僵化的现象。锡铅焊料样品以酒石酸、硝酸、盐酸溶解,采用酒石酸络合掩蔽锡、锑、铋等杂质元素,在pH 6.00的六次甲基四胺缓冲体系中,以二甲酚橙为指示剂,先用EDTA标准滴定溶液滴定了铅、镉总量,再以酒石酸钾钠和邻菲罗啉掩蔽镉,用EDTA标准滴定溶液滴定了铅含量,最后通过差减法计算得到了镉的含量。干扰试验表明,锡铅焊料样品中的杂质元素不干扰测定。方法用于锡铅焊料样品中镉质量分数在10.00%~20.00%的测定,结果与电感耦合等离子体原子发射光谱法(ICP-AES)一致,相对标准偏差(RSD,n=11)为0.28%~0.87%。     

Heavy Metal Removal by Coagulation with Seawater Liquid Bittern

Soluble heavy metals present in water could be deleterious to health, and as a result, their discharge into surface waters has been regulated internationally. Many processes for the removal of heavy metals from water and wastewater have been investigated. Coagulation and precipitation are the processes that have been reported to be most effective in the removal of heavy metals. In this study, seawater liquid bittern (LB), as an inexpensive source of magnesium, added to wastewater alkalized with lime or caustic soda is investigated as a possible coagulant. The experiments covered tests on eight metals: arsenic, cadmium, chromium, copper, lead, mercury, nickel, and zinc. The lime-LB process culminated in high removals (>90%) for cadmium, chromium, lead, mercury, and zinc and reasonably good removals (71, 82, and 75%) for arsenic, copper, and nickel, respectively. These results were superior to those obtained using the caustic-soda–LB process. The concurrent presence of different metals in solution has been shown to have a minor effect on removal efficiencies for most metals. However, in the case of nickel, removal was appreciably increased by 18.5%. Also, higher concentrations of a single metal showed higher removal efficiencies.