The nitritation performance of biofilm reactor for treating domestic wastewater under high dissolved oxygen

The objective of this study was to investigate the nitritation performance in a biofilm reactor for treating domestic wastewater.The reactor was operated in continuous feed mode from phases 1 to 3.The dissolved oxygen(DO)was controlled at 3.5–7 mg/L throughout the experiment.The biofilm reactor showed excellent nitritation performance after the inoculation of nitrifying sludge,with the hydraulic retention time being reduced from 24 to 7 hr.Above 90%nitrite accumulation ratio(NAR)was maintained in phase 1.Afterwards,nitratation occurred with the low NH_4~+–N concentration in the reactor.The improvement of NH_4~+–N concentration to 20–35 mg/L had a limited effect on the recovery of nitritation.However,nitritation recovered rapidly when sequencing batch feed mode was adopted in phase 4,with the effluent NH_4~+-N concentration above 7 mg/L.The improvement of ammonia oxidizing bacteria(AOB)activity and the combined inhibition effect of free ammonia(FA)and free nitrous acid(FNA)on the nitrite oxidizing bacteria(NOB)were two key factors for the rapid recovery of nitritation.Sludge activity was obtained in batch tests.The results of batch tests had a good relationship with the long term operation performance of the biofilm reactor.     

A new process to improve short-chain fatty acids and bio-methane generation from waste activated sludge

As an important intermediate product, short-chain fatty acids(SCFAs) can be generated after hydrolysis and acidification from waste activated sludge, and then can be transformed to methane during anaerobic digestion process. In order to obtain more SCFA and methane,most studies in literatures were centered on enhancing the hydrolysis of sludge anaerobic digestion which was proved as un-efficient. Though the alkaline pretreatment in our previous study increased both the hydrolysis and acidification processes, it had a vast chemical cost which was considered uneconomical. In this paper, a low energy consumption pretreatment method, i.e. enhanced the whole three stages of the anaerobic fermentation processes at the same time, was reported, by which hydrolysis and acidification were both enhanced, and the SCFA and methane generation can be significantly improved with a small quantity of chemical input. Firstly, the effect of different pretreated temperatures and pretreatment time on sludge hydrolyzation was compared. It was found that sludge pretreated at 100°C for 60 min can achieve the maximal hydrolyzation. Further, effects of different initial p Hs on acidification of the thermal pretreated sludge were investigated and the highest SCFA was observed at initial p H 9.0with fermentation time of 6 d, the production of which was 348.63 mg COD/g VSS(6.8 times higher than the blank test) and the acetic acid was dominant acid. Then, the mechanisms for this new pretreatment significantly improving SCFA production were discussed. Finally,the effect of this low energy consumption pretreatment on methane generation was investigated.     

直链烷基苯磺酸盐促进剩余污泥产生短链脂肪酸的研究

采用批试试验的方法研究了十二烷基苯磺酸钠(C12-LAS)对剩余污泥在厌氧发酵过程中产生的短链脂肪酸(SCFAs)的影响.结果表明,C12-LAS的投加极大地提高了剩余污泥厌氧发酵过程中的SCFAs产量.当C12-LAS加入量低于0.1g·g-1时,SCFAs产量随着C12-LAS加入量的增加而增加,然而,当C12-LAS加入量高于0.1g·g-1时,SCFAs产量反而有所降低.从污泥产酸量以及经济成本考虑,C12-LAS的最佳投加量为0.02g·g-1,此时剩余污泥的SCFAs最大产量出现在第6天.进一步的研究表明,C12-LAS不仅促使大量的碳水化合物和蛋白质脱离污泥颗粒并溶解到液相中,而且抑制了产甲烷菌的活性.尽管剩余污泥经历着酸化过程,但由于其释放出大量的NH4 -N,污泥在整个厌氧发酵过程中的pH值逐渐升高.     

盐度强化剩余污泥碱性发酵产酸

短链脂肪酸(SCFAs)是生物脱氮除磷的优质碳源,为提高剩余污泥碱性发酵SCFAs的产量,分别在20℃和35℃条件下,考察了不同盐度(0~25g/L)对剩余污泥碱性(pH=10)发酵的影响.结果表明:在20℃和35℃条件下,投加适量的氯化钠均可提高SCFAs产量,且氯化钠投加量为15g/L时SCFAs产量最大,较不投加时分别提高了42.3%和15.0%.进一步的研究表明,适量的投加氯化钠促进了生成SCFAs所需底物(蛋白质和多糖)的释放,同时提高了发酵系统的C/N(SCFAs/NH4+-N).因此,盐度联合碱性pH值可强化剩余污泥发酵产生SCFAs,同时达到剩余污泥减量的效果.     

柠檬酸钠强化剩余污泥酶水解和酸化的研究

厌氧条件下,研究了阳离子络合剂柠檬酸钠(SC)对剩余污泥酶水解和酸化的影响.结果表明:络合剂SC提高了污泥酶水解和酸化的效率,溶解性蛋白质和碳水化合物溶出量增加,SC的最佳投加剂量为0.432 g·g-1(以TS计,下同).络合剂SC可以提高污泥中短链脂肪酸(SCFAs)的积累量,同时减少达到最大SCFAs积累的时间,缩短厌氧消化时间.空白对照组和蛋白酶组的总SCFAs积累量分别在反应第7 d和第6 d达到最大值,而SC+蛋白酶组(SC 0.432 g·g-1)在反应第2 d就达到了最大值.从酶活性的变化和SEM图可知,SC的投加破坏了EPS的网络结构,原来被束缚、隐藏于污泥基体中的水解酶得到释放,从而提高了污泥水解速率.     

Phosphate recovery from anaerobic digester effluents using CaMg(OH)4

Dolomite lime(DL)(CaMg(OH)_4) was used as an economical source of Mg~(2+)for the removal and recovery of phosphate from an anaerobic digester effluent of a municipal wastewater treatment plant(MWWTP) wastewater. Batch precipitation results determined that phosphate was effectively reduced from 87 to less than 4 mg-P/L when the effluent water was mixed with 0.3 g/L of DL. The competitive precipitation mechanisms of different solids in the treatment system consisting of Ca~(2+)–Mg~(2+)–NH_4~+–PO_4~(3-)CO_3~(2-)were determined by comparing model predictions with experimental results. Thermodynamic model calculations indicated that hydroxyapatite(Ca_(10)(PO_4)_6(OH)_2), Ca_4H(PO_4)_3?3H_2O, Ca_3(PO_4)_2(beta), and Ca_3(PO_4)_2(am2)were more stable than struvite(MgNH_4PO_3?6H_2O) and calcite(CaCO_3). However, X-ray diffraction(XRD) analysis determined the formation of struvite and calcite minerals in the treated effluent. Kinetic experimental results showed that most of the phosphate was removed from synthetic effluent containing NH_4~+within 2 hr, while only 20% of the PO_4~(3-)was removed in the absence of NH_4~+after 24 hr of treatment. The formation of struvite in the DL-treated effluent was due to the rapid precipitation rate of the mineral. The final pH of the DL-treated effluent significantly influenced the mass ratio of struvite to calcite in the precipitates. Because more calcite was formed when the p H increased from 8.4 to 9.6, a p H range of 8.0–8.5 should be used to produce solid with high PO_4~(3-)content. This study demonstrated that DL could be used for effective removal of phosphate from the effluent and that resultant precipitates contained high content of phosphate and ammonium.     

Feasibility of bioleaching combined with Fenton oxidation to improve sewage sludge dewaterability

A novel joint method of bioleaching with Fenton oxidation was applied to condition sewage sludge. The specific resistance to filtration (SRF) and moisture of sludge cake (MSC) were adopted to evaluate the improvement of sludge dewaterability. After 2-day bioleaching, the sludge pH dropped to about 2.5 which satisfied the acidic condition for Fenton oxidation. Meanwhile, the SRF declined from 6.45 × 10¹⁰ to 2.07 × 10¹⁰ s²/g, and MSC decreased from 91.42% to 87.66%. The bioleached sludge was further conditioned with Fenton oxidation. From an economical point of view, the optimal dosages of H₂O₂ and Fe^2 + were 0.12 and 0.036 mol/L, respectively, and the optimal reaction time was 60 min. Under optimal conditions, SRF, volatile solids reduction, and MSC were 3.43 × 10⁸ s²/g, 36.93%, and 79.58%, respectively. The stability and settleability of sewage sludge were both improved significantly. Besides, the results indicated that bioleaching-Fenton oxidation was more efficient in dewatering the sewage sludge than traditional Fenton oxidation. The sludge conditioning mechanisms by bioleaching-Fenton oxidation might mainly include the flocculation effects and the releases of extracellular polymeric substances–bound water and intercellular water.     

基质投加方式对污泥碱性发酵性能的影响

为了研究低温条件(15±2)℃下投加方式对剩余污泥碱性发酵的影响,将剩余污泥分别在NaOH、KOH、Ca(OH)2和混合碱(Ca(OH)2和KOH) 4种碱性(pH=10±0.2)系统中进行发酵,并在系统稳定后依次改变污泥投加方式(1次投加污泥、平均2次投加和平均3次投加),分别对发酵体系的剩余污泥溶液化、溶解性蛋白质、溶解性多糖、挥发性脂肪酸(SCFAs)和关键酶(水解酶和辅酶420(F420))进行研究.研究发现,4种碱性发酵体系中,不同投加方式对剩余污泥的水解和酸化性能具有显著的影响,其中SCOD随着污泥投加次数的增加略有减小,但是发酵液中可溶性的蛋白质和多糖有增加趋势.水解酶活性随着污泥投加次数的增加而降低,但是在NaOH和KOH发酵体系中,辅酶420随着投加次数的增加而增大,混合碱发酵体系中其活性基本不变,而在Ca(OH)2发酵体系中其活性则降低.NaOH、KOH和混合碱发酵体系产酸能力随投加次数的增加而下降,但是Ca(OH)2 发酵体系酸化能力则先增大后少量降低,由此发现,Ca(OH)2发酵体系水解及产酸能力较为稳定,同时该体系中乙酸/SCFAs最大,高于其他发酵体系的10%左右.     

混碱调控剩余污泥碱性发酵实现LDHs高效提取短链脂肪酸

氢氧化钙调控剩余污泥碱性发酵,可有效提高发酵液原位合成层状双金属氢氧化物(LDHs)提取短链脂肪酸(SCFAs)的效率.本文拟利用氢氧化钙和氢氧化钠混碱调控剩余污泥碱性发酵,提高发酵过程SCFAs产量,进一步提高SCFAs提取效率.通过配置不同氢氧化钠和氢氧化钙混合比例的碱液,用于调控剩余污泥碱性发酵实验,发现混碱比例为25∶75时,可避免钙离子对污泥水解产酸影响,发酵液中SCFAs浓度达到6581.4 mg·L~(-1)(以每COD计,下同),是空白对照组(4179.4 mg·L~(-1))的1.6倍.同时,碱液提供的钙离子可将污泥发酵过程释放的无机阴离子去除,CO■、PO■浓度分别低至3.7 mmol·L~(-1)和0.5 mg·L~(-1).利用氢氧化钠和氢氧化钙调控剩余污泥进行混碱厌氧发酵,可有效提高SCFAs的产量,消除主要无机阴离子对发酵液原位合成层状双金属氢氧化物(LDHs)提取SCFAs的干扰,合成的LDHs中SCFAs的含量为52.3 mg·g~(-1) LDHs,是空白组(18.9 mg·g~(-1)LDHs)的2.8倍.     

Advanced treatment of wet-spun acrylic fiber manufacturing wastewater using three-dimensional electrochemical oxidation

A three-dimensional electrochemical oxidation(3D-EC) reactor with introduction of activated carbon(AC) as particle micro-electrodes was applied for the advanced treatment of secondary wastewater effluent of a wet-spun acrylic fiber manufacturing plant. Under the optimized conditions(current density of 500 A/m~2, circulation rate of 5 mL/min, AC dosage of 50 g, and chloride concentration of 1.0 g/L), the average removal efficiencies of chemical oxygen demand(COD_(cr)), NH3–N, total organic carbon(TOC), and ultraviolet absorption at 254 nm(UV_(254)) of the 3D-EC reactor were 64.5%, 60.8%, 46.4%, and 64.8%, respectively; while the corresponding effluent concentrations of COD_(cr), NH_3–N, TOC, and UV_(254) were 76.6, 20.1, and42.5 mg/L, and 0.08 Abs/cm, respectively. The effluent concentration of COD_(cr) was less than 100 mg/L, which showed that the treated wastewater satisfied the demand of the integrated wastewater discharge standard(GB 8978-1996). The 3D-EC process remarkably improved the treatment efficiencies with synergistic effects for COD_(cr), NH_3–N, TOC, and UV_(254) during the stable stage of 44.5%, 38.8%, 27.2%, and 10.9%, respectively, as compared with the sum of the efficiencies of a two-dimensional electrochemical oxidation(2D-EC) reactor and an AC adsorption process, which was ascribed to the numerous micro-electrodes of AC in the 3D-EC reactor. Gas chromatography mass spectrometry(GC–MS) analysis revealed that electrochemical treatment did not generate more toxic organics, and it was proved that the increase in acute biotoxicity was caused primarily by the production of free chlorine.     

Co-fermentation of waste activated sludge with food waste for short-chain fatty acids production: effect of pH at ambient temperature

Effect of pH ranging from 4.0 to 11.0 on cofermentation of waste activated sludge (WAS) with food waste for short-chain fatty acids (SCFAs) production at ambient temperature was investigated in this study. Experimental results showed that the addition of food waste significantly improved the performance of WAS fermentation system, which resulted in the increases of SCFAs production and substrate reduction. The SCFAs production at pH 6.0, 7.0, 8.0, and 9.0 and fermentation time of 4 d was respectively 5022.7, 6540.5, 8236.6, and 7911.7 mg COD·L⁻¹, whereas in the blank tests (no pH adjustment, pH 8.0 (blank test 1), no food waste addition, pH 8.0 (blank test 2), and no WAS addition (blank test 3)) it was only 1006.9, 971.1, and 1468.5 mg COD·L⁻¹, respectively. The composition of SCFAs at pH from 6.0 to 9.0 was also different from other conditions and propionic acid was the most prevalent SCFA, which was followed by acetic and n-butyric acids, while acetic acid was the top product under other conditions. At pH 8.0 a higher volatile suspended solids (VSS) reduction of 16.6% for the mixture of WAS and food waste than the sole WAS indicated a synergistic effect existing in fermentation system with WAS and food waste. The influence of pH on the variations of nutrient content was also studied during anaerobic fermentation of the mixture of WAS and food waste at different pH conditions. The release of NH₄⁺-N increased with fermentation time at all pH values investigated except 4.0, 5.0 and in blank test one. The concentrations of soluble phosphorus at acidic pHs and in the blank test one were higher than those obtained at alkaline pHs. Ammonia and phosphorus need to be removed before the SCFAs-enriched fermentation liquid from WAS and food waste was used as the carbon source.     

Comparison between UV and VUV photolysis for the pre- and post-treatment of coking wastewater

In this study, ultraviolet (UV) and vacuum ultraviolet (VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%–35.4% total organic carbon (TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand (COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD₅/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%–47% TOC within 8 hr irradiation. Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen (NH₄⁺–N), 17% more nitrite nitrogen (NO₂⁻–N), and 18% more total nitrogen (TN) than UV, producing 35% less nitrite nitrogen (NO₃⁻–N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent.     

Effect of organic matter on phosphorus recovery from sewage sludge subjected to microwave hybrid pretreatment

Microwave (MW) hybrid processes are able to disrupt the flocculent structure of complex waste activated sludge, and help promote the recovery of phosphorus as struvite. In this study, to optimize struvite yield, (1) the characteristics of matter released in MW-hybrid treatments were compared, including MW, MW-acid, MW-alkali, MW-H₂O₂, and MW-H₂O₂-alkali. The results showed that selective release of carbon, nitrogen, phosphorus, Ca^2 +, and Mg^2 + achieved by sludge pretreatment using MW-hybrid processes. MW-H₂O₂ is the recommended sludge pretreatment process for phosphorus recovery in the form of struvite. The ratio of Mg^2 +:NH₄⁺-N:PO₄^3 −-P was 1.2:2.9:1 in the supernatant. (2) To clarify the effects of organic matter on struvite recovery, the composition and molecular weight distribution of organic matters were analyzed. Low molecular weight COD was found to facilitate the removal rate of NH₄⁺-N and PO₄³-P via crystallization, and the amorphous struvite crystals (< 1 kDa) from the filtered solutions had high purity. Therefore, the present study reveals the necessity of taking into consideration the interference effect of high molecular weight organic matters during struvite crystallization from sewage sludge.     

New insight into adsorption characteristics and mechanisms of the biosorbent from waste activated sludge for heavy metals

The adsorption characteristics and mechanisms of the biosorbent from waste activated sludge were investigated by adsorbing Pb2+and Zn2+in aqueous single-metal solutions. A p H value of the metal solutions at 6.0 was beneficial to the high adsorption quantity of the biosorbent. The optimal mass ratio of the biosorbent to metal ions was found to be 2. A higher adsorption quantity of the biosorbent was achieved by keeping the reaction temperature below 55°C. Response surface methodology was applied to optimize the biosorption processes, and the developed mathematical equations showed high determination coefficients(above 0.99 for both metal ions) and insignificant lack of fit(p = 0.0838 and 0.0782 for Pb2+and Zn2+, respectively). Atomic force microscopy analyses suggested that the metal elements were adsorbed onto the biosorbent surface via electrostatic interaction. X-ray photoelectron spectroscopy analyses indicated the presence of complexation(between –NH2,-CN and metal ions) and ion-exchange(between –COOH and metal ions). The adsorption mechanisms could be the combined action of electrostatic interaction, complexation and ion-exchange between functional groups and metal ions.     

混合外源菌强化剩余污泥微氧水解产酸

利用外源投加酵母菌与醋酸菌的方式促进了剩余污泥水解产生短链挥发性脂肪酸（SCFAs）的产量,考察了混合投加模式下污泥水解溶出的正磷酸盐、氨氮和溶解性COD的浓度,研究水解过程胞外聚合物（EPS）组分中蛋白质及多糖的变化特征.结果表明,在酵母菌和醋酸菌投加量分别为10和20g/L时,发酵第5d实现了最高的SCFAs产量,达到719mgCOD/gVSS,其中乙酸含量为328.78mgCOD/gVSS,占总SCFAs的45.72%.投加两种菌显著促进了剩余污泥水解产生SCFAs,且以乙酸为主.外源菌投加促进了水解酸化过程氨氮和正磷酸盐的释放,最佳反应条件下最大释放量分别为80.66和22.38mg/gVSS,有利于从剩余污泥中回收氮磷.投加外源菌后EPS中的蛋白质和多糖从内层向最外层释放,为污泥水解产酸提供底物.外源投加酵母菌与醋酸菌是促进剩余污泥水解酸化的有效手段.     

Potential ammonia emission from flag leaves of paddy rice (Oryza sativa L. cv. Koshihikari)

The present study aimed to investigate the potential ammonia (NH₃) emission from flag leaves of paddy rice (Oryza sativa L. cv. Koshihikari). The study was conducted at a paddy field in central Japan that was designed as a free-air CO₂ enrichment (FACE) facility for paddy rice. A dynamic chamber method was used to measure the potential NH₃ emissions. The air concentrations of NH₃ at two heights (2 and 6 m from the ground surface) were measured using a filter-pack method, and the exchange fluxes of NH₃ of the whole paddy field were calculated using a gradient method. The flag leaves showed potential NH₃ emissions of 25-38 ng N cm⁻² h⁻¹ in the daytime from the heading to the maturity stages, and they showed potentials of approximately 22 ng N cm⁻² h⁻¹, even in the nighttime, at the heading and mid-ripening stages. The exchange fluxes of NH₃ of the whole paddy field in the daytime were net emissions of 0.9-3.9 g N ha⁻¹ h⁻¹ whereas the exchange fluxes of NH₃ in the nighttime were approximately zero.     

Effect of aeration rate on composting of penicillin mycelial dreg

Pilot scale experiments with forced aeration were conducted to estimate effects of aeration rates on the performance of composting penicillin mycelial dreg using sewage sludge as inoculation. Three aeration rates of 0.15, 0.50 and 0.90 L/(min·kg) organic matter(OM) were examined. The principal physicochemical parameters were monitored during the 32 day composting period. Results showed that the higher aeration rate of 0.90 L/(min·kg) did not corresponded to a longer thermophilic duration and higher rates of OM degradation;but the lower aeration rate of 0.15 L/(min·kg) did induce an accumulation of NH+4-N contents due to the inhibition of nitrification. On the other hand, aeration rate has little effect on degradation of penicillin. The results show that the longest phase of thermophilic temperatures ≥ 55°C, the maximum NO-3-N content and seed germination, and the minimum C/N ratio were obtained with 0.50 L/(min·kg) OM. Therefore, aeration rates of0.50 L/(min·kg) OM can be recommended for composting penicillin mycelial dreg.     

Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution

A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH₂-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu^2 + adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N₂ adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH₂-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu^2 + on NH₂-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH₂-Mn-SBA-15 for Cu^2 + was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu^2 + by NH₂-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu^2 +. The NH₂-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption–desorption experiments showed that the NH₂-Mn-SBA-15 could be regenerated by acid treatment without altering its properties.     

Particulate matter assessment of a wetland in Beijing

To increase the knowledge on the particulate matter of a wetland in Beijing, an experimental study on the concentration and composition of PM₁₀ and PM_2.5 was implemented in Beijing Olympic Forest Park from 2013 to 2014. This study analyzed the meteorological factors and deposition fluxes at different heights and in different periods in the wetlands. The results showed that the mean mass concentrations of PM₁₀ and PM_2.5 were the highest at 06:00–09:00 and the lowest at 15:00–18:00. And the annual concentration of PM₁₀ and PM_2.5 in the wetland followed the order of dry period (winter) > normal water period (spring and autumn) > wet period (summer), with the concentration in the dry period significantly higher than that in the normal water and wet periods. The chemical composition of PM_2.5 in the wetlands included NH₄⁺, K⁺, Na⁺, Mg^2 +, SO₄^2 −, NO₃⁻, and Cl⁻, which respectively accounted for 12.7%, 1.0%, 0.8%, 0.7%, 46.6%, 33.2%, and 5.1% of the average annual composition. The concentration of PM₁₀ and PM_2.5 in the wetlands had a significant positive correlation with relative humidity, a negative correlation with wind speed, and an insignificant negative correlation with temperature and radiation. The daily average dry deposition amount of PM₁₀ in the different periods followed the order of dry period > normal water period > wet period, and the daily average dry deposition amount of PM_2.5 in the different periods was dry period > wet period > normal water period.     

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect

Batch experiments were conducted to evaluate fluoride removal by Al,Fe,and Ti-based coagulants and adsorbents,as well as the effects of coexisting ions and formation of aluminum–fluoride complexes on fluoride removal by co-precipitation with alum(Al_2(SO_4)_3·18H_2O).Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8.Nano-crystalline TiO_2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3–5.Coexisting anions in water decreased the removal of fluoride in the order:phosphate(2.5 mg/L) arsenate(0.1 mg/L) bicarbonate(200 mg/L) sulfate(100 mg/L) = nitrate(100 mg/L) silicate(10 mg/L) at a pH of 6.0.The effect of silicate became more significant at pH 7.0.Calcium and magnesium improved the removal of fluoride.Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)_3 precipitates from 8.9 to 8.4,indicating the chemical adsorption of fluoride at the surface.The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH 6.5.A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF~(2+),AlF~(+2),and AlF_3complexes.The AlF_x complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.