Enhancing struvite precipitation potential for ammonia nitrogen removal in municipal landfill leachate

This study was conducted to improve struvite precipitation for NH4-N removal purpose in landfill leachate. For this purpose, we evaluated the effect of the feeding sequence of precipitating reagents (magnesium, orthophosphate, and buffering reagent) on NH4-N removal by forming struvite deposits. Struvite precipitation effectively proceeded by an addition of excess magnesium and phosphate sources followed by an addition of the buffering reagent, in which condition the local formation of inappropriate deposits or the contamination of the desired struvite was minimized. We also tested the effect of struvite addition as the seeding materials on NH4-N removal. Seed addition would increase the potential for the struvite crystal growth, which enhanced NH4-N removal performance in landfill leachate treatment.     

Phosphate recovery through struvite precipitation by CO2 removal: effect of magnesium, phosphate and ammonium concentrations

In the present study, the precipitation of struvite (MgNH(4)PO(4)·6H(2)O) using the CO(2) degasification technique is investigated. The precipitation of struvite was done from supersaturated solutions in which precipitation was induced by the increase of the solution supersaturation concomitant with the removal of dissolved carbon dioxide. The effect of magnesium, phosphate and ammonium concentrations on the kinetics and the efficiency of struvite precipitation was measured monitoring the respective concentrations in solution. In all cases struvite precipitated exclusively and the solid was characterized by powder XRD and FTIR. The morphology of the precipitated crystals was examined by scanning electronic microscopy and it was found that it exhibited the typical prismatic pattern of the struvite crystals with sizes in the range between 100 and 300 μm. The increase of magnesium concentration in the supersaturated solutions, resulted for all phosphate concentration tested, in significantly higher phosphate removal efficiency. Moreover, it is interesting to note that in this case the adhesion of the suspended struvite crystals to the reactor walls was reduced suggesting changes in the particle characteristics. The increase of phosphate concentration in the supersaturated solutions, for the magnesium concentrations tested resulted to the reduction of struvite suppression which reached complete suppression of the precipitate formation. Excess of ammonium in solution was found favour struvite precipitation. Contrary to the results found with increasing the magnesium concentration in solution, higher ammonium concentrations resulted to higher adhesion of the precipitated crystallites to the reactor walls. The results of the present work showed that it is possible to recover phosphorus in the form of struvite from wastewater reducing water pollution and at the same time saving valuable resources.     

Treatment of organophosphate-contaminated wastewater by acidic hydrolysis and precipitation

Wastewater from commercial manufacture of organophosphate (OP) pesticide of O-methyl-O-(2-isopropyl salicylate) thiophosphorusyl amide contains large amounts of organophosphate, organic sulfides, COD and NH3-N. A treatment process including acidic hydrolysis and precipitation was explored in this paper. The effects of initial pH values, hydrolysis temperature and hydrolysis time on the removal of pollutants were investigated. The experimental results showed that, in the hydrolysis, with the decreasing initial pH value, the removal of OP, sulfide and COD rose whereas the NH3-N removal declined. Increased hydrolysis temperature and time favored the removal of all the pollutants. 15.0 wt% Ca(OH)2 was sufficient for the removal of inorganic phosphorus and residual NH3-N in the precipitation step. With this chemical process, the removal of total phosphorus (TP), organophosphate, sulfides and NH3-N exceeded 90%, and the removal of COD was about 60%. The BOD5/COD value was greatly improved from 0.05 to 0.3, and the bio-degradability of the wastewater was greatly improved. The NH3 generated in the process was absorbed with water and might be reused in the manufacture of the pesticide. The results showed that this comprehensive process is effective for the treatment of this typical unbio-degradable pesticide wastewater.     

Comparative modeling of biological nutrient removal from landfill leachate using a circulating fluidized bed bioreactor (CFBBR)

Anaerobically digested swine wastewater contains high concentrations of phosphorus (P) and nitrogen (N). A pilot-scale experiment was carried out for nutrients removal and recovery from anaerobically digested swine wastewater by struvite crystallization. In the pilot plant, a sequencing batch reactor (SBR) and a continuous-flow reactor with struvite accumulation devices were designed and employed. The wastewater pH value was increased by CO(2) stripping, and the struvite crystallization process was performed without alkali and Mg(2+) additions. Results of the long-term operation of the system showed that, both reactors provided up to 85% P removal and recovery over wide ranges of aeration times (1.0-4.0 h), hydraulic retention times (HRT) (6.0-15.0 h) and temperatures (0-29.5°C) for an extended period of 247 d, in which approximate 30% of P was recovered by the struvite accumulation devices. However, 40-90% of NH(4)(+)-N removed was through air stripping instead of being immobilized in the recovered solids. The recovered products were detected and analyzed by scanning electron microscope (SEM), X-ray diffraction (XRD) and chemical methods, which were proved to be struvite with purity of more than 90%. This work demonstrated the feasibility and effects of nutrients removal and recovery from anaerobically digested swine wastewater by struvite crystallization without chemical additions.     

Physico-chemical treatments for removal of recalcitrant contaminants from landfill leachate

In this paper, the technical applicability and treatment performance of physico-chemical techniques (individual and/or combined) for landfill leachate are reviewed. A particular focus is given to coagulation-flocculation, chemical precipitation, ammonium stripping, membrane filtration and adsorption. The advantages and limitations of various techniques are evaluated. Their operating conditions such as pH, dose required, characteristics of leachate in terms of chemical oxygen demand (COD) and NH3-N concentration and treatment efficiency are compared. It is evident from the survey of 118 papers (1983-2005) that none of the individual physico-chemical techniques is universally applicable or highly effective for the removal of recalcitrant compounds from stabilized leachate. Among the treatments reviewed in this article, adsorption, membrane filtration and chemical precipitation are the most frequently applied and studied worldwide. Both activated carbon adsorption and nanofiltration are effective for over 95% COD removal with COD concentrations ranging from 5690 to 17,000 mg/L. About 98% removal of NH3-N with an initial concentration ranging from 3260 to 5618 mg/L has been achieved using struvite precipitation. A combination of physico-chemical and biological treatments has demonstrated its effectiveness for the treatment of stabilized leachate. Almost complete removal of COD and NH3-N has been accomplished by a combination of reverse osmosis (RO) and an upflow anaerobic sludge blanket (UASB) with an initial COD concentration of 35,000 mg/L and NH3-N concentration of 1600 mg/L and/or RO and activated sludge with an initial COD concentration of 6440 mg/L and NH3-N concentration of 1153 mg/L. It is important to note that the selection of the most suitable treatment method for landfill leachate depends on the characteristics of landfill leachate, technical applicability and constraints, effluent discharge alternatives, cost-effectiveness, regulatory requirements and environmental impact.     

Treatment of landfill leachate by using electro-Fenton method

In this study, the effects of various operating conditions such as treatment time, DC current, initial pH, initial H(2)O(2) concentration and distance between the electrodes on treatability of landfill leachate by using electro-Fenton (EF) method were examined. The settling characteristics of waste sludge produced from the treatment were also determined. According to the results, EF method can be used efficiently for the treatment of landfill leachate by using the proper operating conditions. The best removal efficiencies were obtained when: treatment duration is 20 min, constant DC current value is 3A, H(2)O(2) concentration is 2000 mg L(-1) and the initial pH value is 3. For these conditions, 72% COD, 90% color, 87% PO(4)-P and 28% NH(4)-N removals were obtained. It was also observed that using electrode distance between 1.8 cm and 2.8 cm increases efficiency of the COD removal, significantly. Sedimentation characteristics of the waste sludge produced from the EF method is fairly good.     

Removal of organic pollutants from 2,2',5,5'-tetrachlorobenzidine (TCB) industrial wastewater by micro-electrochemical oxidation and air-stripping

A feasible method for treatment of the wastewater from the two-staged neutralization in 2,2',5,5'-tetrachlorobenzidine (TCB) manufacturing processes, a refractory dye intermediate effluents, based on combined micro-electrochemical oxidation or iron-chipping filtration (ICF) and air-stripping reactor (ASR), was developed. On conditions of HRT 1h, pH 3.0 in ICF and HRT 38 h, gas-liquid ratio 15, pH 6.0-8.65, temperature 26 degrees C in ASR, the overall COD, color, TCB and NH(4)(+)-N removal were 96.8%, 91%, 87.61% and 62%, respectively, during the treatment of TCB wastewater from the two-staged neutralization dissolved by methanol. The averaged 18.3%, 81.7% of the total degraded COD, 35.2%, 64.8% of TCB were carried out in ICF and ASR, respectively. NH(4)(+)-N removal was finished mainly in ASR. The experimental results indicated that the combined micro-electrochemical oxidation and air-stripping process performed good treatment of COD, color, TCB and NH(4)(+)-N removal in TCB wastewater from the two-staged neutralization dissolved by ethanol or acetone, came up the discharge standard in China. But the TCB wastewater from the two-staged neutralization dissolved by methanol should be deeply treated before discharged.     

Use of magnesit as a magnesium source for ammonium removal from leachate

Using magnesit (MgCO(3)) as a low cost source of magnesium ions in the struvite precipitation for the removal of high ammonium content of leachate was evaluated. Optimum molar concentration and pH conditions were analyzed to minimize the struvite solubility. Since solubility of magnesit in water is low, HCl was used to obtain soluble Mg. Maximum soluble Mg was obtained for the addition of 2 M HCl to the 1 M MgCO(3). Struvite precipitation with magnesit was effective for the removal of ammonium, suspended solid, phosphate and turbidity. Economical evaluation was made comparing the costs of two magnesium sources, MgCl(2) and MgCO(3). The economical analysis has shown that operation cost of struvite precipitation can be reduced about 18% by using MgCO(3) instead of MgCl(2). High salt concentration after struvite precipitation has no inhibitory effect on the anaerobic reactor performance.     

Characteristics and mechanisms of phosphate adsorption onto basic oxygen furnace slag

The adsorption characteristics of phosphate adsorption on the basic oxygen furnace (BOF) slag were identified as a function of pH and ion strengths in solution. In addition, adsorption mechanisms were investigated by conducting batch tests on both the hydrolysis and phosphate adsorption process of the BOF slag, and making a comparative analysis to gain newer insights into understanding the adsorption process. Results show that the adsorption capacity from 4.97 to 3.71 mgP/g slag when the solution pH was increased from 2.0 to 13.0 and phosphate initial concentration was 50 mg/L, indicating that adsorption capacity is largely dependent upon the pH of the system. The results of the competitive adsorption between phosphate and typical anions found in wastewater, such as NO(3)(-), SO(4)(2-) and Cl(-), onto BOF slag reveal that BOF slag can selectively adsorb phosphate ions. The insignificant effect of NO(3)(-), SO(4)(2-) and Cl(-) on phosphate adsorption capacity indicates that phosphate adsorption is through a kind of inner-sphere complex reaction. During the adsorption process, the decrease of phosphate concentration in solution accompanied with an increase in pH values and concentrations of NO(3)(-), SO(4)(2-) and Cl(-) suggests that phosphate replaced the functional groups from the surface of BOF slag which infers that ligand exchange is the dominating mechanism for phosphate removal. At the same time, the simultaneous decreases in PO(4)(3-) and total calcium, magnesium and aluminum concentration in solution indicate that chemical reaction and precipitation are other mechanisms of phosphate removal.     

Simultaneous removal of phenol, ammonium and thiocyanate from coke wastewater by aerobic biodegradation

A laboratory-scale activated sludge plant composed of a 20 L volume aerobic reactor followed by a 12 L volume settling tank and operating at 35 degrees C was used to study the biodegradation of coke wastewater. The concentrations of ammonium nitrogen (NH(4)(+) -N), phenols, chemical oxygen demand (COD) and thiocyanate (SCN(-)) in the wastewater ranged between 504 and 2,340, 110 and 350, 807 and 3,275 and 185 and 370 mg/L, respectively. The study was undertaken with and without the addition of bicarbonate. The addition of this inorganic carbon source was necessary to favour nitrification, as the alkalinity of the wastewater was very low. Maximum removal efficiencies of 75%, 98% and 90% were obtained for COD, phenols and thyocianates, respectively, without the addition of bicarbonate. The concentration of ammonia increased in the effluent due to both the formation of NH(4)(+) as a result of SCN(-) biodegradation and to organic nitrogen oxidation. A maximum nitrification efficiency of 71% was achieved when bicarbonate was added, the removals of COD and phenols being almost similar to those obtained in the absence of nitrification. Batch experiments were performed to study the influence of pH and alkalinity on the biodegradation of phenols and thiocyanate.     

Chemical denitrification of water by zero-valent magnesium powder

A laboratory-scale study was conducted in batch mode to investigate the feasibility of using zero-valent magnesium (Mg(0)), for removal of nitrate from aqueous solution. Reaction pH, dose of Mg(0), initial nitrate concentration and temperature were considered variable parameters during the study. Strong acidic condition enhanced nitrate reduction and in absence of external proton addition, reaction pH increased rapidly above ten and insignificant nitrate removal (7-16%) was achieved. At Mg(0):NO(3)(-)-N molar ratio of 5.8 and controlled reaction pH of 2, 84% denitrification efficiency was achieved (initial NO(3)(-)-N 50 mg/L) under ambient temperature and pressure and total nitrogen removal was 70% with 3.2% and 10% conversion of initial NO(3)(-)-N to NO(2)(-)-N and NH(4)(+)-N, respectively. The reaction was first order with respect to nitrate concentration. Nitrate removal rate decreased with solution pH and increased linearly with Mg(0) dose. Nitrate removal was coupled with 96-100% removal of dissolved oxygen and 85-90% generation of soluble Mg(2+) ion. An activation energy (E(a)) of nitrate reduction over the temperature range of 10-50 degrees C was observed as 17.7 kJ mol(-1).     

Laboratory investigations of stormwater remediation via slag: Effects of metals on phosphorus removal

The use of electric arc furnace (EAF) slag for the removal of phosphorus (P) from various simulated stormwater blends was investigated in the laboratory. The form of P measured was the inorganic orthophosphate (PO(4)-P). The stormwater solutions used in this preliminary study were synthesized as blends of P and typical concentrations of some of the most common and abundant metals in stormwater (e.g. cadmium, copper, lead and zinc), and contacted with EAF slag to determine P removal efficiency and sorptive competition. Results showed that the presence of cadmium, lead and zinc had minimal effect on the removal process; copper was a significant inhibitor of P uptake by the EAF slag media. P removal was greatest in the metal-free and multi-metal stormwater solutions.     

Recovery of struvite from animal wastewater and its nutrient leaching loss in soil

Contaminants in swine wastewater were recovered in the form of struvite, a crystal of magnesium ammonium phosphate (MAP), using a newly designed process, and the leaching loss of MAP in soil was examined. The continuous flow process was operated under optimal conditions: 1.0 molar ratio of magnesium (Mg) addition with respect to orthophosphate (OP) and an aeration rate of 0.73 L/L min. Five treatments were performed with three replications for soil pH and nutrient leaching loss tests. It was found that 93% of the OP in the swine wastewater was crystallized, and the MAP crystal formation was verified by X-ray diffraction (XRD) and scanning electron microscope (SEM) analyses. The analyses revealed that the pattern of pH change and N leaching losses for MAP-treated soil were remarkably different from those for fused super phosphate (FSP)-urea-treated soils. The pH levels for the control and FSP-urea-treated soils after a five-week experiment were unchanged or slightly decreased, whereas an increase in pH was observed in the MAP-treated soils. Leaching loss of N was higher in FSP-urea treatments, with MAP treatments showing N losses of only 1.93 and 2.05%, respectively, while FSP-urea treatments showed N losses of 7.82 and 6.47%, respectively, during the same period. Phosphate (P) leaching was very slow in both MAP- and FSP-treated groups.     

Tertiary treatment of textile wastewater with combined media biological aerated filter (CMBAF) at different hydraulic loadings and dissolved oxygen concentrations

An up-flow biological aerated filter packed with two layers media was employed for tertiary treatment of textile wastewater secondary effluent. Under steady state conditions, good performance of the reactor was achieved and the average COD, NH(4)(+)-N and total nitrogen (TN) in the effluent were 31, 2 and 8mg/L, respectively. For a fixed dissolved oxygen (DO) concentration, an increase of hydraulic loading resulted in a decrease in substrate removal. With the increase of hydraulic loadings from 0.13 to 0.78m(3)/(m(2)h), the removal efficiencies of COD, NH(4)(+)-N and TN all decreased, which dropped from 52 to 38%, from 90 to 68% and from 45 to 33%, respectively. In addition, the results also confirmed that the increase of COD and NH(4)(+)-N removal efficiencies resulted from the increase of DO concentrations, but this variation trend was not observed for TN removal. With the increase of DO concentrations from 2.4 to 6.1mg/L, the removal efficiencies of COD and NH(4)(+)-N were 39-53% and 64-88%, whenas TN removal efficiencies increased from 39 to 42% and then dropped to 35%.     

Chemical precipitation and biosorption treating landfill leachate to remove ammonium-nitrogen

Using chemical precipitation and biosorption to recovery the NH₄ ⁺-N from landfill leachate had been studied. Under optimum conditions of pH 10, contact time 30 min, Mg/N/P molar ratio 1:1:1 for chemical precipitation in which initial NH₄ ⁺-N concentration of 610–640 mg/L was achieved by NH₄ ⁺-N removals around 88 %. And using banana peels (BPs) and modified biosorbent (NMBPs) to further purify the water containing NH₄ ⁺-N was carried out. The experimental results showed that the NMBPs can greatly improve the sorption removal for NH₄ ⁺-N. The pH value was an important parameter in NH₄ ⁺-N removal. The residue NH₄ ⁺-N was 4.5–5.8 mg/L, which can meet the “standard for pollution control on the landfill site of municipal solid waste” (GB16889-2008). Based on X-ray diffraction analysis, chemical precipitation filter residue was compared with commercial MAP, which showed that the precipitate has the similar crystal structure with MAP. Fourier transform infrared absorption spectrum analysis of BPs, NMBPs before and after sorption revealed the active of hydroxyl groups at the surface of BPs have been strengthened after modified; and nitrogenous groups appeared after biosorpting the NH₄ ⁺-N.     

Nitritation and denitritation of ammonium-rich wastewater using fluidized-bed biofilm reactors

Fluidized-bed biofilm nitritation and denitritation reactors (FBBNR and FBBDR) were operated to eliminate the high concentrations of nitrogen by nitritation and denitritation process. The dissolved oxygen (DO) concentration was varied from 1.5 to 2.5 g/m(3) at the top of the reactor throughout the experiment. NH(4)-N conversion and NO(2)-N accumulation in the nitritation reactor effluent was over 90 and 65%, respectively. The average NH(4)-N removal efficiency was 99.2 and 90.1% at the NLR of 0.9 and 1.2 kg NH(4)-N/m(3)day, respectively. Increasing the NLR from 1.1 to 1.2 kg NH(4)-N/m(3)day decreased the NH(4)-N elimination approximately two-fold while NH(4)-N conversion to NO(2)-N differences were negligible. The NO(2)-N/NO(x)-N ratios corresponded to 0.74, 0.73, 0.72, and 0.69, respectively, indicating the occurrence of partial nitrification. An average free ammonia concentration in the FBBNR was high enough to inhibit nitrite oxidizers selectively, and it seems to be a determining factor for NO(2)-N accumulation in the process. In the FBBDR, the NO(x)-N (NO(2)-N+NO(3)-N) concentrations supplied were between 227 and 330 mg N/l (NLR was between 0.08 and 0.4 kg/m(3)day) and the influent flow was increased as long as the total nitrogen removal was close to 90%. The NO(2)-N and NO(3)-N concentrations in the effluent were 3.0 and 0.9 mg/l at 0.08 kg/m(3)day loading rate. About 98% removal of NO(x)-N was achieved at the lowest NLR in the FBBDR. The FBBDR exhibited high nitrogen removal up to the NLR of 0.25 kg/m(3)day. The NO(x)-N effluent concentration never exceeded 15 mg/l. The total nitrogen removal efficiency in the FBBRs was higher than 93% at 21+/-1 degrees C.     

Influence of alkyl sulfates on waste activated sludge fermentation at ambient temperature

Alkyl sulfates (AS), such as sodium dodecyl sulfate (SDS), are widely used in household and industrial products, and can be found in some wastewater and waste activated sludge (WAS). The effect of SDS on the fermentation of WAS at ambient temperature was investigated in this paper. Experimental results showed that the concentrations of protein and carbohydrate in aqueous phase increased with the amount of SDS. The concentrations of both NH(4)(+)-N and PO(4)(3-)-P in fermentation liquor also increased in the presence of SDS. In addition, it was observed that the fermentative short-chain fatty acids (SCFAs) concentration was affected by SDS. With the increase of SDS dosage, the maximum SCFAs concentration increased, and the fermentation time before reaching the maximum SCFAs concentration also increased. Further investigation showed that the produced SCFAs consisted of acetic, propionic, n-butyric, iso-butyric, n-valeric and iso-valeric acids, and acetic, iso-valeric and propionic acids were the three main products. The influence of SDS on methanogenesis was also investigated, and the inhibitory effect of SDS on methanogens activity was observed.     

Effect of anions on removing Cu2+, Mn2+ and Zn2+ in electrocoagulation process using aluminum electrodes

In the present study, the performance of electrocoagulation process with aluminum electrodes in the treatment of Cu(2+), Zn(2+) and Mn(2+) containing aqueous solutions was investigated by depending on type of anion in solution, considering some operating conditions such as initial metal concentration and pH. Results obtained from synthetic wastewater showed that type of anion in solutions has a significant effect on the metal removal. The initial concentration of zinc influenced significantly the performance of electrocoagulation process as compared with the results obtained from Mn and Cu metals. Anions studied did not generate an important difference between pH variations. Best removals for three metals were achieved with increasing the pH in the presence of both anions. Total removals of copper and zinc reached almost 100% after 5 min at pH values > 7. At the end of the experiments for 35 min, the Mn removals were 85 and 80% in the presence of sulfate and chloride anions, respectively.     

Study of the aerobic biodegradation of coke wastewater in a two and three-step activated sludge process

A laboratory-scale biological plant composed of two aerobic reactors operating at 35 degrees C was used to study the biodegradation of coke wastewater. The main pollutants to be removed are organic matter, especially phenols, thiocyanate and ammonium nitrogen. The concentrations of the main pollutants in the wastewater during the study ranged between 922 and 1,980 mg COD/L, 133 and 293 mg phenol/L, 176 and 362 mg SCN/L and 123 and 296 mg NH(4)(+)-N/L. The biodegradation of these pollutants was studied employing different hydraulic residence times (HRT) and final effluent recycling ratios in order to minimize inhibition phenomena attributable to the high concentrations of pollutants. During the optimisation of the operating conditions, the removal of COD, phenols and thiocyanate was carried out in the first reactor and the nitrification of ammonium took place in the second. The best results were obtained when operating at an HRT of 98 h in the first reactor and 86 h in the second reactor, employing a recycling ratio of 2. The maximum removal efficiencies obtained were 90.7, 98.9, 98.6 and 99.9% for COD, phenols, thiocyanate and NH(4)(+)-N, respectively. In order to remove nitrate, an additional reactor was also implemented to carry out the denitrification process, adding methanol as an external carbon source. Very high removal efficiencies (up to 99.2%) were achieved.     

Utilization of steel-making slag for the uptake of ammonium and phosphate ions from aqueous solution

Steel-making slag, a waste by-product of the Steel Industry, constitutes a major disposal problem. In the present study, excellent adsorbent materials for reducing eutrophication in wastewaters have been prepared from this slag. Heated samples of acid-treated slag and mixtures of slag with kaolinite and Al(OH)(3) were examined to determine their uptake capacities for NH(4)(+) and PO(4)(3-) from aqueous solutions. In general, the equilibrium pH of the solution increased in comparison to initial pH with the uptake of target ions, the sample activated slag-Al(OH)(3) showing the smallest change. The highest PO(4)(3-) uptake capacity was obtained with the slag-Al(OH)(3) mixture heated at 900 degrees C whereas the highest uptake of NH(4)(+) was found in the slag-Al(OH)(3) mixture heated at 800 degrees C. The uptake rates for PO(4)(3-) and NH(4)(+) by the slag-Al(OH)(3) mixture heated at 900 degrees C were 2.91 and 0.65 micro mol/(g min), respectively. It was shown that heating slag composites prior to incorporation into wastewater treatment filters resulted in an increased degree of NH(4)(+) and PO(4)(3-) uptake.