A combination of ion exchange and electrochemical reduction for nitrate removal from drinking water. Part II: electrochemical treatment of a spent regenerant solution.

The process of electrochemical treatment of a solution after strong basic anion exchanger regeneration was studied. The goal of the study was to reduce the nitrate content in the solution to allow its use in a closed loop. Diaphragmless, flow-through cells in a recirculation mode with and without a fluidizing bed of inert particles in the interelectrode space equipped with copper (Cu) cathodes and activated titanium anodes were used. The temperature was maintained at 20 degrees C. To assess the influence of recirculation of the regenerant solution on the quality of the treated water, the effect of the addition of copper ions to the solution, postelectrolysis cathode treatment, and enhanced mass transfer on the electrolysis results with respect to current efficiency and residual nitrate and nitrite concentration were investigated using an artificial solution. On the basis of the experimental results, a laboratory-scale unit for selective nitrate removal was designed and constructed that integrated ion exchange and electrochemical cell to one assembly. The process of recirculation of regenerant solution was tested using groundwater.     

The ability of Azolla caroliniana to remove heavy metals (Hg(II), Cr(III), Cr(VI)) from municipal waste water

The aim of this paper was to investigate the capacity of a small water fern, Azolla caroliniana Willd. (Azollaceae), to purify waters polluted by Hg and Cr. Many plants are capable of accumulating heavy metals (called hyperaccumulators) and one of them is the water fern A. caroliniana. During 12 days of the experiment the fern was grown on the nutrient solution containing Hg2+, Cr3+ and CrO4(2-) ions, each in a concentration 0.1, 0.5 and 1.0 mg dm(-3). The presence of these ions caused a 20-31% inhibition of A. caroliniana growth, the highest in the presence of Hg(II) ions, in comparison to the control. After day 12 of the experiment, metal contents the solution decreased to 0-0.25 mg dm(-3), and this decrease comprised between 74 (Cr3+ 1.0 mg dm(-3) treatment) and 100% (CrO4(2-) 0.1 mg dm(-3) treatment). The fern took a lesser quantity of the metals from 0.1 mg dm(-3) treatments compared to 0.5 and 1.0 mg dm(-3) treatments. In the A. caroliniana tissues the concentration of heavy metals under investigation ranged from 71 to 964 mg kg(-1) dm; the highest level being found for Cr(III) containing nutrient solution.     

Hydroxyl radical scavenging role of chloride and bicarbonate ions in the H2O2/UV process

Simultaneous effect of inorganic anions, such as chloride and bicarbonate ions, on the scavenging of hydroxyl radicals (HO*) in the H2O2/UV process is the focus of this paper. The model compound of n-chlorobutane (BuCl) was used as the probe of HO*. By changing the pH conditions (2-9) and the concentrations of NaCl (0.25-2500 mM) and NaHCO3 (25 mM), the variation of HO* concentrations and the rate of H2O2 decomposition were compared. In general, the BuCl and H2O2 follow closely the first-order reaction within the first 10 and 40 min, respectively. In the presence of chloride alone at the pH range of 2-6, the HO* concentration in the reaction mixture increases with the increase of pH, and the HO* concentration at pH = 6 is 100 times of that at pH = 2. Including bicarbonate species in the solution, the peak HO* concentration was found at a certain pH, which shifts from 4, 5, to 5-7, as the molar ratios of chloride/bicarbonate species increase from 1 to 100. In addition, without bicarbonate species HO* concentration decreases significantly with increasing chloride concentration but remained rather unchanged beyond 1250 mM. In contrast, the HO* scavenging in the presence of bicarbonate species became relatively significant only when the chloride concentration reached beyond 250 mM. Throughout all experiments of different water quality conditions, the H2O2 decomposition rate remains rather unchanged.     

Particulate nitrate measurement using nylon filters

Nylon filters are a popular medium to collect atmospheric fine particles in different aerosol monitoring networks, including those operated by the U.S. Environmental Protection Agency and the Interagency Monitoring of Protected Visual Environments (IMPROVE) program. Extraction of the filters by deionized water or by a basic aqueous solution (typically a mixture of sodium carbonate and sodium bicarbonate) is often performed to permit measurement of the inorganic ion content of the collected particles. Whereas previous studies have demonstrated the importance of using a basic solution to efficiently extract gaseous nitric acid collected using nylon filters, there has been a recent movement to the use of deionized water for extraction of particles collected on nylon filters to eliminate interference from sodium ion (Na+) during ion chromatographic analysis of inorganic aerosol cations. Results are reported here from a study designed to investigate the efficiency of deionized water extraction of aerosol nitrate (NO3-) and sulfate from nylon filters. Data were obtained through the conduct of five field experiments at selected IMPROVE sites. Results indicate that the nylon filters provide superior retention of collected fine particle NO3-, relative to Teflon filters, and that deionized water extraction (with ultrasonication) of collected NO3- and sulfate is as efficient, for the situations studied, as extraction using a basic solution of 1.7 mM sodium bicarbonate and 1.8 mM sodium carbonate.     

Mobilization of arsenic from subsurface sediments by effect of bicarbonate ions in groundwater

Arsenic leaching by bicarbonate ions has been investigated in this study. Subsurface sediment samples from Bangladesh were treated with different carbonate and bicarbonate ions and the results demonstrate that the arsenic leaching efficiency of the carbonate solutions decreased in the order of Na2CO3>NaHCO3>BaCO3>MnCO3. Sodium carbonate and bicarbonate ions extracted arsenic most efficiently; Na2CO3 leached maximum 118.12 microg/l of arsenic, and NaHCO3, 94.56 microg/l of arsenic from the Ganges delta sediments after six days of incubation. The arsenic concentrations extracted in the batch experiments correlated very well with the bicarbonate concentrations. The kinetics study of arsenic release indicates that arsenic-leaching rate increased with reaction time in bicarbonate solutions. Bicarbonate ions can extract arsenic from sediment samples in both oxic and anoxic conditions. A linear relationship found between arsenic contents in core samples and those in leachates suggests that dissolved arsenic concentration in groundwater is related to the amount of arsenic in aquifer sediments. In batch experiment, bicarbonate solutions effectively extracted arsenic from arsenic adsorbed iron oxyhydroxide, reflecting that bicarbonate solutions may mobilize arsenic from iron and manganese oxyhydroxide in sediments that are ubiquitous in subsurface core samples. Carbonate ion may form complexes on the surface sites of iron hydroxide and substitute arsenic from the surface of minerals and sediments resulting in release of arsenic to groundwater. Like in the batch experiment, arsenic and bicarbonate concentrations in groundwater of Bangladesh correlated very well. Therefore, bicarbonate leaching is presumed to be one important mechanism to mobilize arsenic in bicarbonate dominated reducing aquifer of Bangladesh and other parts of the world as well.     

Artificial acidification of a non-acidic and an acidic headwater stream in Maine, USA

Two headwater streams with low DOC and different pHs (4.5-4.8 and 5-6.5) were acidified with H2SO4 to pH 4.1 and 4.5, respectively, for 24-h periods. Neutralization of the added acid occurred by protonation of ANC (HCO3-dominated in the higher pH stream), desorption of Ca (< 15 microeq litre(-1)) and Mg (<6 microeq litre(-1)), and desorption and dissolution of AL (<250 microg litre(-1)) from the stream bed. The concentrations of dissolved organic carbon (DOC) remained constant within the experimental reaches. The concentrations of Na, K an H4SiO4 also remained constant, indicating no detectable increase in the rate of chemical weathering in the stream bed. After acid addition was stopped, concentrations of Ca, Mg and Al decreased to below background, indicating reversible ion exchange as the principal mechanism for the mobility of Ca and Mg and to a lesser extent for Al. Repeated acidifications indicated that significant regeneration of cations on the exchange surfaces of the stream substrate occurs rapidly.     

Fluoride removal performance of a novel Fe-Al-Ce trimetal oxide adsorbent

A trimetal oxide was developed as a fluoride adsorbent by coprecipitation of Fe(II), Al(III) and Ce(IV) salt solutions with a molar ratio of 1:4:1 under alkaline condition. The material retained amorphous structure and maintained relatively stable fluoride adsorption performance at calcination temperatures lower than 600 degrees C. The optimum pH range for fluoride adsorption was 6.0-6.5 and the adsorbent also showed high defluoridation ability around pH 5.5-7.0, which is preferable for actual application. A high fluoride adsorption capacity of 178 mg g(-1) was acquired under an equilibrium fluoride concentration of 84.5 mg l(-1), adsorbent dose of 150 mg l(-1) and pH 7.0. The adsorption isotherm could be better described by the two-site Langmuir model than the one-site model, suggesting the existence of two types of active sites on the adsorbent surface. Coexistence of high concentrations of phosphate or arsenate only led to partial inhibition of fluoride adsorption, which further suggests the existence of heterogeneous adsorption sites. Sulfate and chloride did not affect fluoride adsorption, and nitrate influenced it only when the concentration of NO(3)(-)-N exceeded 50 mg l(-1). A high desorption efficiency of 97% was achieved by treating fluoride loaded Fe-Al-Ce oxide with NaOH solution at pH 12.2. A column experiment using the adsorbent fabricated into 1mm pellets was performed at an initial fluoride concentration of 5.5 mg l(-1), space velocity of 5h(-1) and pH of 5.8, and 2240 bed volumes were treated with the effluent fluoride under 1.0 mg l(-1).     

污泥中重金属的去除及回收试验

论述了利用离子交换技术循环使用柠檬酸去除污泥中重金属,并置换回收重金属的适宜工艺条件.经柠檬酸处理后,污泥中90%以上的重金属被去除;柠檬酸处理液中的重金属用离子交换法回收,考察了树脂种类、流速、操作方式等因素对离子交换、再生效果的影响;在适宜工艺条件下,重金属的交换率均为100%,而洗脱率均接近90%;柠檬酸及离子交换树脂循环使用,重金属也得到回收,降低了处理成本.     

Enhanced removal of arsenic from a highly laden industrial effluent using a combined coprecipitation/nano-adsorption process

Effective arsenic removal from highly laden industrial wastewater is an important but challenging task. Here, a combined coprecipitation/nano-adsorption process, with ferric chloride and calcium chloride as coprecipitation agents and polymer-based nanocomposite as selective adsorbent, has been validated for arsenic removal from tungsten-smelting wastewater. On the basis of operating optimization, a binary FeCl₃ (520 mg/L)–CaCl₂ (300 mg/L) coprecipitation agent could remove more than 93 % arsenic from the wastewater. The resulting precipitate has proved environmental safety based on leaching toxicity test. Fixed-bed column packed with zirconium or ferric-oxide-loaded nanocomposite was employed for further elimination of arsenic in coprecipitated effluent, resulting in a significant decrease of arsenic (from 0.96 to less than 0.5 mg/L). The working capacity of zirconium-loaded nanocomposite was 220 bed volumes per run, much higher than that of ferric-loaded nanocomposite (40 bed volumes per run). The exhausted zirconium-loaded nanocomposite could be efficiently in situ regenerated with a binary NaOH–NaCl solution for reuse without any significant capacity loss. The results validated the combinational coprecipitation/nano-adsorption process to be a potential alternative for effective arsenic removal from highly laden industrial effluent.     

Modeling of electrodialytic and dialytic removal of Cr, Cu and As from CCA-treated wood chips

A one-dimensional model is developed for simulating the electrodialytic and dialytic treatment of a saturated bed of wood chips containing chromium, copper and arsenic. The movement of Cr, Cu and As is mathematically modeled taking into account the diffusion transport resulting from the concentration gradients of their compounds and the electromigration of their ionic, simple and complex species during the operation. The model also includes the electromigration of the non-contaminant principal ionic species in the system, H(+) and OH(-), proceeding from the electrolysis at the electrodes, Na(+) and NO(3)(-) used as electrolyte solutions in the electrode compartments, and oxalate ions and protons incorporated with the oxalic acid solution during wood chips incubation. The model simulation also takes into account that OH(-) generated on the cathode, during electrodialytic remediation, is periodically neutralized by addition of nitric acid in the cathode compartment. The anion and cation-exchange membranes are simply represented as ionic filters that preclude the transport of co-ions (the cations and anions respectively) with the exception of H(+), which is retarded but considered to pass through the anion-exchange membrane.     

锆负载型树脂用于含氟废水深度处理的研究

本文研制了一种以火力发电厂废树脂为载体的锆负载型氟离子吸附剂 ,并在评价了该树脂对氟离子的吸附性能之后探讨了该树脂用于火力发电厂含氟废水深度处理的可能性。研究结果表明 ,锆的最佳负载的最佳浓度为0 .5mol/L ,该负载树脂的最佳吸附pH为 3.0— 4 .0 ,用填充柱进行的动态实验结果表明 ,pH =3时的吸附容量显著高于 pH=4时的值。利用该树脂对火力发电厂模拟含氟废水进行了双柱串联吸附工艺处理 ,当柱流量为 35mL/min(SV10 )、第二柱穿透时 ,第一柱的吸附容量为 10 2 2 8mg/L湿树脂 ;用 0 .1mol/L的NaOH溶液进行再生 ,柱流量选择为 35mL/min(SV10 )时 ,脱附率在 95 %以上。     

Column study of Cr(VI) removal by cationic hydrogel for in-situ remediation of contaminated groundwater and soil

Column experiments were conducted for examining the effectiveness of the cationic hydrogel on Cr(VI) removal from groundwater and soil. For in-situ groundwater remediation, the effects of background anions, humic acid (HA) and pH were studied. Cr(VI) has a higher preference for being adsorbed onto the cationic hydrogel than sulphate, bicarbonate ions and HA. However, the adsorbed HA reduced the Cr(VI) removal capacity of the cationic hydrogel, especially after regeneration of the adsorbents, probably due to the blockage of adsorption sites. The Cr(VI) removal was slightly influenced by the groundwater pH that could be attributed to Cr(VI) speciation. The 6-cycle regeneration and reusability study shows that the effectiveness of the cationic hydrogel remained almost unchanged. On average, 93% of the adsorbed Cr(VI) was recovered in each cycle and concentrated Cr(VI) solution was obtained after regeneration. For in-situ soil remediation, the flushing water pH had an insignificant effect on the release of Cr(VI) from the soils. Multiple-pulse flushing increased the removal of Cr(VI) from the soils. In contrast, more flushing water and longer operation may be required to achieve the same removal level by continuous flushing.     

Influence of some groundwater and surface waters constituents on the degradation of 4-chlorophenol by the fenton reaction

The Fenton reaction has been applied to the degradation of 4-chlorophenol in aqueous solutions containing various anions. The rate of the reaction was found to decrease in the following order of anions (at the same concentrations): CIO (4) ~ NO (3)- > SO(4) (2-) > CI(-)> >HPO(4) (2-) > HCO(3)(-). Degradation of the pollutant containing the above anions at concentrations typical of those found in groundwater and surface waters was affected in a similar way. The results are discussed in terms of the effects of these anions on the rates of the oxidation of ferrous anion as well as on their role in the scavenging of hydroxyl radical     

Protective effects of sodium bicarbonate on murine ochratoxicosis

The protective effect of sodium bicarbonate (NaHCO3), a urine modifier, to alleviate murine ochratoxicosis was investigated. The study included two trials. Urinary pH was altered before oral administration of ochratoxin A (OA) in Trial 1, and animals were given combined doses of OA and ethyl biscoumacetate (Eb) in Trial 2. Acute toxicity of OA as measured by LD50 values was reduced by 23% and 20% in rats treated with NaHCO3 for Trials 1 and 2 respectively. Bicarbonate-treated rats dosed with 20 mg/kg OA or with a combination dose of OA at 17 mg/kg and Eb at 50 mg/kg, had a lower frequency of histological lesions in kidneys, liver, lung, spleen and heart. Two types of heart lesions found in the present study are described.     

Size fractionated speciation of nitrate and sulfate aerosols in a sub-tropical industrial environment

Size fractionated chemical speciation of acidic aerosols were performed for ammonium sulfate, other sulfates, ammonium nitrate and other nitrates in a sub-tropical industrial area, Bina, India during December 2003 to November 2004. Analysis of variance (ANOVA) revealed highly significant temporal variations (p > .001) in the concentrations of nitrate and sulfate aerosols in all the three size fractions (fine, mid-size and coarse). Winter demonstrated utmost concentrations of ammonium sulfate, which ranged from 3.2 to 26.4 microg m(-3) in fine particles and 0.20-0.34 microg m(-3) in coarse particles. Ammonium sulfate was chiefly in fine mode (43.77% of total particulate sulfate) as compared to coarse particles (28.60% of total particulate sulfate). The major fraction Ammonium sulfate existed in different forms in atmospheric aerosols, for example NH4Fe(SO4)2, (NH4)2SO4, (NH4)3H(SO4)2 in fine particles, and (NH4)4(NO3)SO4+ in coarse particles. Other sulfate concentrations were also higher during winter ranging from 1.89 to 14.3 microg m(-3) in fine particles and 0.12-0.65microg m(-3) in coarse particles. Ammonium nitrate constituted the major fraction of total particulate nitrate all through the year and was principally in fine particles (the highest concentration in January i.e. 14.2 microg m(-3)). Other nitrates were mainly distributed in the fine particles (highest concentration in January i.e. 11.2 microg m(-3)) All the sulfate and nitrate species were mainly distributed in fine mode and have significant impact on human health.     

The negative rejection of H+ in NF of carbonate solution and its influences on membrane performance

Nanofiltration (NF) experiments were conducted with simulated solution containing bicarbonate hardness and with three membranes: NF90, NF270 and NF-. The operating pressure was kept at 1.0 MPa, the water sample temperature was kept at 25 degrees C, the velocity on membrane surface was approximately 1 m s(-1) and the feeding pH values were 6.0, 6.5, 7.0, 7.5 and 8.0. Except for sampling, both the concentrate and the permeate were cycled to the feeding tank in order to keep the concentration constant. Experimental results demonstrated that the flux of NF90 membrane was slightly affected by the feeding pH, while the flux of NF270 and NF membranes was augmented when the feeding was acidified. The permeate pH of each membrane was always lower than the concentrate pH, indicating that the H(+) was negative rejected. This phenomenon was observed not only in the filtration of carbonate solution, but also in the filtration of the NaCl solution and the tap water. It is assumed that the small positive H(+) can easily permeate the NF membranes having negative charges. The more charges the membrane has, the more H(+) is negative rejected. High permeability of H(+) can speed decomposition of HCO(3)(-) into CO(3)(2-) and then accelerate CaCO(3) crystallization on membrane surface, which is unfavorable for membrane performances. In NF processes, it is better to considerate the membrane's selection and the feeding's pretreatment simultaneously, and it is beneficial for preventing scaling when selecting the membranes with less negative charges if only the water qualify can meet the demands.     

平板炭气凝胶电极电吸附除氟

采用自制的炭气凝胶平板电极进行模拟水样中氟的电吸附去除研究,通过单因子实验优化了该电吸附技术的操作参数和适用的溶液条件,并研究了反接电极法的再生效果。研究结果表明,自制的炭气凝胶平板由纳米颗粒组成三维网络结构,比表面积为670.90 m2/g,具有良好的充放电可逆性和迅速形成表面双电层的特点。静态电吸附除氟效果最佳的条件为:水样氟离子浓度6 mg/L,pH 7.0,极板间距4 cm,电压1.6 V;共存物质硝酸根、腐殖酸、碳酸根和碳酸氢根等对氟离子的电吸附具有一定的促进作用。吸附氟离子后的炭气凝胶材料的比表面、孔体积、电容值有所减小。对于吸附氟离子后的炭气凝胶平板电极,采用反接电极法取得较好再生效果的条件为:流动状态、电压1.6 V、极板间距4 cm。再生后的炭气凝胶电极与原始炭气凝胶相比,依然具有良好的充放电可逆性。     

Assessment of the effect of the toxicity of a textile dye on Nostoc muscorum ISU, a diazotrophic cyanobacterium

The impact of graded concentrations (5, 10, 15 and 20 mg dm(-3) of acid mordant Metomega Chrome Orange GL, a common dye used in woollen, carpet and textile industries, was studied on protein and pigment content and photosynthetic oxygen evolution in a diazotrophic cyanobacterium Nostoc muscorum. The lower concentration of 5 mg dm(-3) showed a negligible effect on protein and pigment content and photosynthetic oxygen evolution, whereas at higher concentrations a drastic decrease in the above parameters was observed. The highest concentration of 20 mg dm(-3) resulted in a decrease of protein, chlorophyll a, phycocyanin and carotenoid content by 72, 76, 54 and 17% of the control, respectively. Photosynthetic oxygen evolution also decreased by 92% of the control at this concentration of the dye.     

Denitrification of nitrate wastewater using packed-bed columns.

Columnar packed-bed (PB) reactors with a specific surface area of 127 m2/m3 were investigated in this study for treating nitrate wastewater. This study demonstrated that a single-stage packed bed was able to achieve total nitrogen (TN) and chemical oxygen demand (COD) removal efficiencies higher than 83 and 75%, respectively. The highest achievable TN and COD removal rates were 47.2 g N/m2 x d and 158.0 g COD/m2 x d, respectively. The substrate removal rate in the PB column was found to follow half-order reaction kinetics, with a reaction coefficient, kappa, of 53.62 (mg/L)1/2/d. A dual-stage PB system was capable of achieving TN and COD removal efficiencies greater than 99 and 98%, respectively. Effluent TN and COD concentrations less than 6.5 mg NO3(-)-N/L and 50.0 mg COD/L, respectively, were obtained when the dual PB system was used.     

Ion exchange treatment of rinse water generated in the galvanizing process.

A study was conducted of the viability of using the cationic exchange resins Amberlite IR-120 and Lewatit SP-112 to treat rinse water generated in the galvanizing process as well as acidic wastewater containing zinc (Zn) and iron (Fe). Solutions containing either 100 mg/L of Zn at pH 5.6 (rinse water) or Fe and Zn at concentrations of 320 and 200 mg/L at pH 1.5 (acidic water), respectively, were percolated through packed beds until the resins were exhausted. Breakthrough capacities obtained ranged between 1.1 and 1.5 meq metal/mL resin. The elution of metal and the regeneration of resins were performed with hydrochloric acid. The influence of the flowrate used during the loading stage was also studied, with 0.5 bed volumes/min (3.2 cm/min) found to be the optimum flowrate.