Removal of Heavy Metals from Automotive Wastewater by Sulfide Precipitation

The United States Environmental Protection Agency has proposed new categorical pretreatment effluent standards for the Metal Products and Machinery Industry, which are more stringent than current discharge limits in the automotive industry. Therefore, this study was conducted to evaluate metal-sulfide precipitation chemistry as an alternative to metal-hydroxide precipitation chemistry for removing Cu, Ni, Pb, and Zn. There were three aspects of this study: (1) theoretical analysis of both metal–hydroxide and metal–sulfide chemistry; (2) experimental evaluation of commercially available sulfur-containing precipitants using deionized water; and (3) experimental evaluation of the precipitants using wastewater samples from three automotive manufacturing plants (transmission, engine, and assembly plants). The primary findings are: (1) In theory, metal–hydroxide chemistry can achieve the proposed standards when no chelating agents are present. This is not true when as small as 1 mg/L of ethylenediaminetetra-acetic acid (EDTA) is present. (2) Metal–sulfide precipitation chemistry could achieve solubility limits lower than those of metal–hydroxide chemistry over a wide range of pH. However, EDTA could still inhibit precipitation of Ni, Pb, and Zn to concentrations above the proposed standards. (3) The experiments with wastewater samples showed all precipitants removed Cu well while Ni and Zn were not well removed. The sample from transmission and engine plants were more difficult to treat than from an assembly plant, suggesting that it might have had more chelating agents. The commercially available precipitants did not perform any better than sodium sulfide. (4) Costs for using the precipitants were estimated to range from <$1/1,000 gal to >$5/1,000 gal depending on the precipitant.     

Sorption of Cr (VI) onto Olive Stone in a Packed Bed Column: Prediction of Kinetic Parameters and Breakthrough Curves

This paper investigates the ability of olive stone to remove chromium (VI) ions from aqueous solution in a packed bed up-flow column with an internal diameter of 1.5 cm. The experiments were performed with a bed height of 15 g (13.4 cm) and a flow rate of 2 mL/min. To predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design, four kinetic models; Adams-Bohart, Thomas, Yoon-Nelson, and Dose-Response models were applied to the experimental data. All models were found suitable for describing the whole or a definite part of the dynamic behavior of the column. The simulation of the whole breakthrough curve was effective with the Dose-Response model, but the initial part of the breakthrough was best predicted by the Adams-Bohart model. On the other hand, the results indicated that, at pH values of this work, approximately 50% of Cr (VI) is biosorbed by olive stone and the other 50% is reduced to Cr (III), both processes being of equal importance. Therefore, a two-stage biosorption process was developed. The goal of these final experiments was to confirm that Cr (III) [the Cr (VI) reduction product] was also effectively sorbed by olive stone in a second column.     

Evaluation of Electrokinetic Removal of Heavy Metals from Tailing Soils

Electrokinetic remediation was studied for the removal of toxic heavy metals from tailing soils. The study emphasized the dependency of removal efficiencies upon their speciations, as demonstrated by the different extraction methods used, which included sequential extraction, total digestion, and 0.1 N HCl extraction. The tailing soils examined showed different physicochemical characteristics, such as initial pH, particle size distribution, and major mineral constituents, and they contained high concentrations of target metal contaminants in various forms. The electrokinetic removal efficiencies of heavy metals were significantly influenced by their partitioning prior to treatment, and the pHs of the tailing soils. The mobile and weakly bound fractions of heavy metals, such as the exchangeable fraction, were easily removed by electrokinetic treatment (more than 90% removal efficiency), but immobile and strongly bound fractions, such as the organically bound species and residual fractions, were not significantly removed (less than 20% removal efficiencies).     

Heavy Metals Removal from Acidic and Saline Soil Leachate Using Either Electrochemical Coagulation or Chemical Precipitation

This study compares electrocoagulation and chemical precipitation for heavy metals removal from acidic soil saline leachate (SSL) at the laboratory pilot scale. The electrocoagulation process was evaluated via an electrolytic cell [12 cm (width)×12 cm (length)×19 cm (depth)] using mild steel electrodes (10 cm width×11 cm high), whereas chemical precipitation was evaluated using either calcium hydroxide [Ca(OH)2] or sodium hydroxide (NaOH). By comparison with chemical precipitation at a pH varying between 7 and 8, electrocoagulation was more effective in removing metals from SSL having a relatively low contamination level (124?mg?Pb/L and 38?mg?Zn/L). For SSL enriched with different heavy metals (each concentration of metals was initially adjusted to 100 mg/L) and treated at a pH lower than 8.5, with the exception of Cd, the residual metal concentrations at the end of the experiments were below the acceptable level recommended for effluent discharge in urban sewage works (less than 4 mg/L of each residual metal concentration was recorded) using electrocoagulation, contrary to chemical precipitation using NaOH (more than 15 mg/L of each residual metal concentration was recorded). By comparison, chemical precipitation using Ca(OH)2 was effective in reducing Cr, Cu, Ni, and Zn under the permissive level, but not for Cd and Pb. However, both chemical precipitation processes needed to be operated at higher pH values (around 10.0) to be more effective in reducing metals from SSL and, therefore, required a pH adjustment of the effluent before discharge, whereas electrochemical treatment had a practical advantage of producing an effluent having a pH close to the neutral value and suitable for stream discharge in the receiving water. On the other hand, electrocoagulation was also found to be very efficient for removing Pb from very contaminated solutions (250–2,000 mg?Pb/L). At least 94% of Pb was removed regardless of the initial Pb concentration in the SSL. Electrochemical coagulation involves a total cost varying from 8.67 to 13.00 $/tds, whereas 0.84 to 16.73 $/tds is recorded using chemical precipitation. The cost included only energy consumption, chemicals consumption, and metallic sludge disposal.     

New Approach: Waste Materials as Sorbents for Arsenic Removal from Water

The sorption of inorganic arsenic species (arsenite and arsenate) from aqueous solutions onto steel-mill waste and waste filter sand, under neutral conditions, was investigated in this study. Additionally, the steel-mill waste material was modified in order to minimize its deteriorating impact on the initial water quality and to meet the drinking water standards. The influence of contact time and initial arsenic concentration was investigated using batch system techniques. To evaluate the application for real groundwater treatment, the capacities of the obtained waste materials were further compared to those exhibited by commercial sorbents, which were examined under the same experimental conditions. Kinetic studies revealed that waste slag materials are the most efficient in arsenic removal, reaching equilibrium arsenic sorption capacities in the range 47.6–55.2?μg/g, while waste filter sand exhibited capacities of 25.4–29.8?μg/g (for an initial arsenic concentration Co = 0.5?mg/L). The higher iron content in the slag materials was considered to be responsible for the better removal efficiencies, and the specific arsenic removal efficiency was estimated to be 220?μgAs/gFe. The specific arsenic removal efficiency of the second active substance found in waste filter sand, manganese, was estimated to be 115?μgAs/gMn. Equilibrium studies revealed the occurrence of both chemisorption and physical sorption processes. All the waste materials exhibited higher performances for As(V). The highest maximum sorption capacity was obtained by waste iron slag: 4040?μg/g for As(V). The waste materials reached the arsenic removal capacities of the examined commercial materials, suggesting the feasibility of their application in real groundwater treatment.     

Storm Water Detention Ponds: Modeling Heavy Metal Removal by Plant Species and Sediments

Laboratory and field studies were conducted to elucidate heavy metal removal by three wetland grasses and sediments in storm water detention pond. The removal of heavy metals including Cd, Cu, Pb, and Zn was mediated by fluid-flow intensity in the reactors. The growth of plants and the removal rates of contaminants were plant species dependent. All three wetland grasses removed contaminants from the spiked nutrient solutions. A first-order kinetic model adequately represented the removal of contaminants by plants. The analyses of undisturbed sediment cores in detention pond revealed strong stratification of heavy metal concentrations at the sediment–water interface. A simple model that integrates heavy metal removal by aquatic plants and sediments in storm water detention ponds is proposed. The model provides an estimate of contaminant residence time which can be related to hydraulic residence time in storm water detention ponds.     

Removal of Zn2+ from Electroplating Wastewater Using Modified Wood Sawdust and Sugarcane Bagasse

This paper describes the preparation of new adsorbents derived from sugarcane bagasse and wood sawdust (Manilkara sp.) to remove zinc (II) ions from electroplating wastewater. The first part deals with the chemical modification of sugarcane bagasse and wood sawdust, using succinic anhydride to introduce carboxylic acid functions into the material. The obtained materials (modified sugarcane bagasse MB2 and modified wood sawdust MS2) were then characterized by infrared spectroscopy (IR) and used in adsorption experiments. The adsorption experiments evaluates Zn2+ removal from aqueous single metal solution and real electroplating wastewater on both batch and continuous experiments using fixed-bed columns prepared in laboratorial scale with the obtained adsorbents. Adsorption isotherms were then developed using Langmuir model and the Thomas kinetic model. The calculated Zn2+ adsorption capacities were found to be 145?mg/g for MS2 and 125?mg/g for MB2 in single metal aqueous solution, whereas for the industrial wastewater these values were 61?mg/g for MS2 and 55?mg/g for MB2.     

Lead Removal from Acidic Solutions by Sorption on Cocoa Shells: Effect of Some Parameters

The objectives of this work were to evaluate the effects of different parameters (Pb concentration, solution pH, Ca/Mg/Na/K salt concentrations) on Pb uptake by cocoa shells and to study the mechanisms of Pb removal in very acidic conditions. Sorption tests were conducted in shaken flasks with synthetic Pb solutions and 15 g/L cocoa shells. A lead uptake value of 161 mmol/kg was measured during the assay with [Pb]i = 3.66?mmol/L in solution at pHi = 2.0 and T = 22°C. Results show that Pb uptake is very similar (14.5–16.0 mmol/kg) for an initial pH between 2.0 and 4.0, but a moderate decrease (10.8 mmol/kg) occurred when the initial pH=1.5 and the [Pb]i = 0.25?mmol/L. High Ca and Mg concentrations (2.35 mol/L) in solution induced a significant decrease in Pb removal by cocoa shells, whereas high K and Na concentrations did not affect Pb uptake by this sorbent. This suggests that Pb uptake by cocoa shells is controlled by ion-exchange reactions with Ca/Mg ions and protons. Finally, chemical tests have shown that carboxyl and amine functional groups play a dominant role in Pb uptake by cocoa shells.     

Removal of Mercury from Low-Concentration Aqueous Streams Using Chemical Reduction and Air Stripping

Field, laboratory, and engineering data confirmed the efficacy of chemical reduction and air stripping as a low concentration mercury treatment concept for water containing Hg(II). The process consists of dosing the water with low levels of stannous chloride [Sn(II)] to convert the mercury to elemental mercury (Hg0). Hg0 can easily be removed from the water by air stripping or sparging. We studied this concept for groundwater containing initial mercury concentrations of approximately 138 ng/L (0.00069 μmol/L). In undosed samples, sparging removed 0% of the initial mercury. Removal in the treated samples varied by reagent dose. Low reagent doses, with Sn:Hg stoichiometric ratios <1, showed little removal. High reagent doses, with Sn:Hg stoichiometric ratios greater than about 5 to 25, showed relatively complete removal (>94%) and yielded final mercury concentrations <10 ng/L (<0.00005 μmol/L). At intermediate doses, mercury removal was a function of the dose. A kinetic study indicated that addition of the Sn(II) reagent resulted in rapid reduction of Hg(II) to Hg0. When combined with standard supporting engineering techniques (e.g., treating the purge air) as needed, a simple system of chemical reduction and stripping may be useful and cost effective.     

Removal of Nickel(II) from Dilute Aqueous Solution by Sludge-Ash

This work examines the adsorption of Ni(II) onto sludge–ash, a waste produced from a fluidized bed incinerator combusted primarily with biosolids. Results of kinetic experiments showed that the adsorption was rapid. The kinetic adsorption data can be well described by an empirical modified Freundlich equation. The rate of adsorption decreased with either increasing surface loading and ionic strength or decreasing solution pH. The results of equilibrium studies showed that the solution pH was the key factor affecting the adsorption. The modified Langmuir model fit revealed that the hydrogen ion acts as a competitive inhibitor for the adsorption of Ni onto ash. The maximum adsorption capacity for Ni is 5.41 μmol/g. Experimental results indicate that the adsorption is favorable at higher temperature. Thermodynamic adsorption parameters for ΔG°, ΔH°, and ΔS° are ?7.41 kcal/mol, 7.25 kcal/mol, and 48.9 cal/mol?K, respectively.     

Optimization of Internal Bypass Ratio for Complete Ammonium and Phosphate Removal in a Dephanox-Type Two-Sludge Denitrification System

The capacity of complete simultaneous ammonium and phosphate removal was studied in a laboratory scale Dephanox system in relation to its internal bypass ratio (BPR). In this configuration, most of the ammonium detected in the effluent is ammonium bypassed by the system’s internal settler. Therefore, this research studies the possibility of complete simultaneous ammonium and phosphate removal by means of the balance of bypassed ammonium with ammonium requirement for growth of denitrifying phosphorus accumulating organisms in the anoxic tank. During these experiments, ammonium removal was governed by internal BPR and limited by sludge settleability. The predominant anaerobic-anoxic sludge developed a high settleability, allowing the application of drastic low BPRs. The system studied under many BPRs proved to achieve almost complete simultaneous ammonium and phosphate removal for BPRs ranging from 0.08 to 0.13 of the influent. A BPR lower than the inferior limit produced extreme accumulation of sludge into the internal settler, interfering in the distribution of sludge and consequently in removal efficiency. A positive effect of the internal settler was the extension of anaerobic contact time and anaerobic solids retention time. The increased phosphorus release suggests that a higher volatile fatty acids production might have occurred when raw wastewater was used as influent.     

离子交换树脂吸附锰(Ⅱ)的热力学和动力学研究

采用静态吸附法,研究了D113离子交换树脂吸附锰(Ⅱ)的过程和机理。结果表明:在一定的浓度范围内,D113树脂对锰(Ⅱ)的吸附符合Langmuir和Freundlich等温吸附方程式,但Langmuir方程更能准确反映该交换吸附过程。热力学函数ΔH0,表明吸附为放热反应,降低温度有利于吸附进行;ΔS0,说明吸附过程熵减少占主导作用;ΔG0,表明该吸附过程为自发过程。吸附交换过程符合HO准二级吸附交换动力学方程,表观吸附活化能Ea为35.085 kJ/mol,颗粒扩散过程为吸附的控速步骤。     

Aerated Rock Filters for Enhanced Ammonia and Fecal Coliform Removal from Facultative Pond Effluents

Rock filters used to treat effluents from waste stabilization ponds do not remove ammonia as they are anoxic. A pilot-scale aerated rock filter was investigated, in parallel with an unaerated control, over an 18-month period to determine whether aeration provided conditions within the rock filter for nitrification to occur. Facultative pond effluent containing ～ 10?mg NH4–N/L was applied to the filters at a hydraulic loading rate of 0.15?m3/m3?day during the first 8?months and at 0.3?m3/m3?day thereafter. The results show that the ammonia and nitrate concentrations in the effluent from the aerated filter were <3 and ～ 5?mg?N/L, respectively, whereas the ammonia concentration in the effluent from the control filter was ～ 7?mg?N/L. Fecal coliforms were reduced in the aerated filter to a geometric mean count of 65?per?100?mL; in contrast the effluent from the control filter contained 103–104 fecal coliforms per 100?mL. Aerated rock filters are thus a useful land-saving alternative to aerobic maturation ponds.     

Selective Removal of Heavy Metals from Industrial Wastewater Using Maghemite Nanoparticle: Performance and Mechanisms

This study investigated the applicability of maghemite (γ-Fe2O3) nanoparticles for the selective removal of toxic heavy metals from electroplating wastewater. The maghemite nanoparticles of 10?nm were synthesized using a sol–gel method and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The surface area of the nanoparticles was determined to be 198?m2/g using the Brunauer–Emmett–Teller method. Batch experiments were carried out to determine the adsorption kinetics and mechanisms of Cr(VI), Cu(II), and Ni(II) by maghemite nanoparticles. The adsorption process was found to be highly pH dependent, which made the nanoparticles selectively adsorb these three metals from wastewater. The adsorption of heavy metals reached equilibrium rapidly within 10?min and the adsorption data were well fitted with the Langmuir isotherm. Regeneration studies indicated that the maghemite nanoparticles undergoing successive adsorption–desorption processes retained original metal removal capacity. Mechanism studies using TEM, XRD, and X-ray photoelectron spectroscopy suggested that the adsorption of Cr(VI) and Cu(II) could be due to electrostatic attraction and ion exchange, and the adsorption of Ni(II) could be as a result of electrostatic attraction only.     

Removal of Cr(VI) ions from aqueous solution using foundry waste material: Kinetic and equilibrium studies

Abstract

In the present paper, Cr(VI) ions removal from aqueous solutions by adsorption on waste mould (green) sand was investigated. Waste mould sand is byproduct of the grey iron foundry. Batch adsorption test was carried out to determine the removal characteristic for Cr(VI) ions from aqueous solution. The obtained results are promising in the use of waste mould sand as an efficient low cost and non-conventional adsorbent for the removal of Cr(VI) ions from aqueous solutions. The second order kinetics produced better fitting of results in terms of correlation coefficient which suggests that the adsorption kinetics of Cr(VI) ions on the waste mould sand followed the second order kinetic model. In the isotherm studies, Freundlich, Langmuir, Dubin–Radushevich and Redlich–Peterson isotherm models were applied and it was determined that the experimental data conformed to Langmuir isotherm model.

Dans cet article, on examine l’enlèvement d’ions Cr(VI) de solutions aqueuses par adsorption sur le sable (vert) à moulage résiduel. Le sable à moulage résiduel est un sous-produit de la fonderie de fonte grise. On a effectué un essai d’adsorption en discontinu afin de déterminer les caractéristiques d’enlèvement des ions Cr(VI) d’une solution aqueuse. Les résultats obtenus sont prometteurs quant à l’utilisation du sable à moulage résiduel comme adsorbant efficace non conventionnel et à faible coût pour l’enlèvement des ions Cr(VI) de solutions aqueuses. La cinétique de second ordre a produit un meilleur ajustement des résultats par rapport au coefficient de corrélation, ce qui suggère que la cinétique d’adsorption des ions Cr(VI) sur le sable à moulage résiduel suivait le modèle cinétique de second ordre. Dans les études d’isothermes, on a appliqué les modèles d’isotherme de Freundlich, Langmuir, Dubin, – Radushevich et Redlich – et de Peterson et l’on a déterminé que les données expérimentales se conformaient au modèle d’isotherme de Langmuir.     

Development of a Response Surface for Prediction of Nitrate Removal in Sulfur–Limestone Autotrophic Denitrification Fixed-Bed Reactors

Sulfur–limestone autotrophic denitrification (SLAD) processes are very efficient for treatment of ground or surface water contaminated with nitrate. However, detailed information is not available on the interaction among some major variables on the design and performance of the SLAD process. In this study, the response surface method was used by designing a rotatable central composite test scheme with 12 SLAD column tests. A polynomial linear regression model was set up to quantitatively describe the relationship of the effluent and influent nitrate–nitrogen concentration and hydraulic retention time (HRT) in the SLAD column reactors. This model may be used for estimating the effluent nitrate–nitrogen concentration when the influent nitrate–nitrogen concentration ranges between 20 and 110?mg/L and the HRT ranges between 2 and 9?h. Based on our model and the requirement for nitrite control, we recommend that the HRT of the SLAD column reactor be kept ≥ 6?h and the nitrate loading rate less than 200 g NO3?–N/day?m3 media to achieve high nitrate removal efficiency (>99%) and prevent nitrite accumulation from being >1?mg/L NO2?–N.     

Development and Evaluation of a Copolymer for Removal of Taste and Odor Causing Compounds from Lake Michigan Water

In this study, a copolymer, cyclodextrin/epichlorohydrin was synthesized and used as an adsorbent to remove two taste and odor causing compounds, namely, MIB and geosmin from the Lake Michigan water. The removal efficiency of these compounds using the copolymer on average was 74.5% for MIB and 77.5% for geosmin as compared to the removal efficiency using powdered activated carbon that resulted in 52.9% and 67% removal, respectively, for the same compounds. The removal efficiencies were examined for an initial concentration range of 20 to 120?μg/L for both MIB and geosmin.     

Design and Operation of Point-of-Use Treatment System for Arsenic Removal

A point-of-use (POU) system was designed and constructed using commercially available activated alumina to remove arsenic from drinking water. Testing with City of Albuquerque chlorinated tap water containing an average of 23 ug/L arsenic found that 1 L of adsorbent would provide water for direct consumption by a family of four for 435 days. It was estimated that the POU system constructed for this study could be sold for $162, and the arsenic adsorption columns were estimated to cost $4. A monthly cost to the customer of $10/month was estimated to purchase, install, and operate this POU system, assuming annual replacement of adsorption media cartridges. The implications of relying upon POU systems to comply with a new drinking water standard for arsenic are discussed.     

Removal of Metal Ions from Storm-Water Runoff by Low-Cost Sorbents: Batch and Column Studies

The possibility of using the sorption technology to reduce the levels of metal ions present in urban storm-water runoff was investigated in this study. Seven sorbent materials including Amberlite XAD7, chitosan, crab shell, peat, Sargassum, sawdust, and sugarcane bagasse were initially examined for removal of 11 metal ions (Na, K, Ca, Mg, Mn, Co, Ni, Cu, Zn, Cd, and Pb) from simulated storm-water runoff at different concentrations. Among these sorbents, crab shell performed well with removal efficiencies exceeding 93% for all heavy metal ions examined and thus selected for further studies. Based on scanning electron microscopy/energy-dispersive x-ray analysis, microprecipitation of metal carbonates followed by adsorption onto the surface of crab shell was identified as the major mechanism responsible for removal of heavy metal ions by crab shell. Crab shell exhibited rapid removal of meal ions with attainment of biosorption equilibrium within 20 min. A crab-shell-packed column was used to study the continuous metal retention process. The column performed very well in the removal of heavy metal ions and was able to operate up to 192 h at a flow rate of 10 mL/min before outlet concentrations of Mn and Co reached 0.3 times of their respective inlet concentrations. Other metal ions such as Pb, Zn, Ni, Cd, and Cu were only in trace levels in the final effluent until 192 h. These findings would form the basis for the future development of crab-shell-based biofilters for removal of dissolved heavy metal ions from storm-water runoff.     

Carbon Adsorption and Air-Stripping Removal of MTBE from River Water

Through 1998, methyl tertiary-butyl ether (MTBE) was the most commonly used fuel oxygenate in Reno, Nevada. Winter-use of oxygenated gasolines is required in areas of the country that exceed carbon monoxide air quality standards. MTBE has not been detected in Reno’s raw water sources, but treatment alternatives must be assessed to fully prepare for possible contamination events. In this research, bench-scale studies using activated carbon and air stripping were conducted to evaluate the treatability of a high concentration of MTBE in Truckee River water, which is the primary surface supply for the Reno area. Results indicated that neither method appears practical for treating MTBE-laden water for one day at a 1.14×108?L/day (30 MGD) treatment plant. The capital costs estimated for full-scale application of these processes are approximately $5 million each. Estimated treatment costs for activated carbon and air stripping are approximately $0.043/L ($0.161/gal) and $0.047/L ($0.177/gal), respectively. Temporary closure of treatment facilities may be the best response to an accidental spill.