工业废水中溴离子对COD测定的影响

研究了工业废水中高浓度溴离子对COD测定的干扰，考察了有机物浓度、溴离子浓度与表观COD值之间的关系，并初步探索了隐蔽溴离子的方法。结果表明，当溴离子浓度一定时，有机物浓度越低，溴离子对表观COD值的贡献越大；当有机物浓度一定时，溴离子浓度越小，单位质量溴离子对COD的贡献越大；含溴废水中有机物的实际COD可通过表观COD与Br^-对COD的贡献值之差进行估算。试验还发现，硫酸汞不能消除溴离子对COD测定的干扰；硝酸铬和硫酸铝也不能有效地隐蔽溴离子。     

Effect of inorganic constituents on chemical oxygen demand—I. Bromides are unneutralizable by mercuric sulfate complexation

Chemical oxygen demand (COD) assays are widely used for the estimation of the organic carbon content of water and wastewater. The procedure is subject to interference by free halogen ions, the oxidation of which creates artificially high COD values. As part of an investigation of the interferences involved in the COD determination of chemical industries wastewaters, we found that mercuric sulfate complexation, the standard procedure for neutralizing the halogen effects, is suitable for chlorides but is not applicable to bromides. This observation is true both in the presence or absence of chloride or ammonia. Care should therefore be exercised in the interpretation of COD data for bromide-containing samples.     

Technical note: interference of Br-, BrO3-, and ClO3- with DOX determination

In the dissolved organic halogen (DOX) analytic test, prior to combustion, the granular activated carbon (GAC) on which the DOX is absorbed is washed with a sodium nitrate solution designed to remove any inorganic chloride that may have also adsorbed to the GAC. Thus, a potential positive interference is removed. This study investigated the effectiveness of the nitrate wash in eliminating possible interferences from bromide, bromate, and chlorate ions. No interference was detected from bromate or chlorate ion, but a small positive interference of about 12 micrograms Cl-/L per mg/L of bromide ion was found in the presence of background organic matter.     

Evaluation and improvement of total organic bromine analysis with respect to reductive property of activated carbon

A collective parameter and a toxicity indicator for all the halogenated organic disinfection byproducts in a water sample is total organic halogen (TOX), which can be differentiated as total organic chlorine (TOCl), total organic bromine (TOBr) and total organic iodine. The TOX method involves concentration of organic halogens from water by adsorption onto activated carbon (AC). A previous study showed that a portion of TOCl can be reduced to chloride during the adsorption procedure, which can be minimized by ozonation of the AC. In this study, a portion of TOBr was sometimes found to be reduced by AC to bromide, and the reduction was generally less than that of corresponding TOCl. The results suggested that around 10% of brominated Suwannee River fulvic acid was reduced to bromide. However, some brominated amino compounds (especially glycylglycine, phenylalanine, and cytosine) were found to be more reactive with the AC. For the iodinated compounds studied, the reduction to iodide was not significant. The method for the TOBr measurement was improved by using ozonated AC when reduction occurred on the original AC. The improved method was also evaluated on treated wastewater and swimming pool water samples.     

A pilot-scale evaluation of magnetic ion exchange treatment for removal of natural organic material and inorganic anions

The objective of this research was to evaluate a magnetic ion exchange process (MIEX) for the removal of natural organic material (NOM) and bromide on a continuous-flow pilot-scale basis under different operating conditions and raw water characteristics. The most important operating variable was the effective resin dose (ERD), which is the product of the steady-state resin concentration in the contactor and the regeneration ratio. The raw water employed in this study had a moderate concentration of ultraviolet (UV)-absorbing substances and dissolved organic carbon (DOC), and a low turbidity, alkalinity, and concentration of competing anionic species. Experiments were conducted using the ambient raw water and raw water spiked with bromide, chloride, and sulfate. Substantial removal of UV-absorbing substances and DOC was achieved at ERDs as low as 0.16mL/L. Moderate bromide removal was achieved, depending on the ERD. Increasing the sulfate concentration resulted in decreased removal of UV-absorbing substances, DOC, and bromide. Consistent results were observed between the continuous-flow pilot plant tests and batch equilibrium studies.     

Removal of bromide and natural organic matter by anion exchange

Bromide removal by anion exchange was explored for various water qualities, process configurations, and resin characteristics. Simulated natural waters containing different amounts of natural organic matter (NOM), bicarbonate, chloride, and bromide were treated with a polyacrylate-based magnetic ion exchange (MIEX) resin on a batch basis to evaluate the effectiveness of the resin for removal of bromide. While bromide removal was achieved to some degree, alkalinity (bicarbonate), dissolved organic carbon (DOC), and chloride were shown to inhibit bromide removal in waters with bromide concentrations of 100 and 300 μg/L. Water was also treated using a two-stage batch MIEX process. Two-stage treatment resulted in only a slight improvement in bromide removal compared to single-stage treatment, presumably due to competition with the high concentration of chloride which is present along with bromide in natural waters. In view of the relatively poor bromide removal results for the MIEX resin, a limited set of experiments was performed using polystyrene resins. DOC and bromide removal were compared by treating model waters with MIEX and two polystyrene resins, Ionac A-641 and Amberlite IRA910. The two polystyrene resins were seen to be more effective for bromide removal, while the MIEX resin was more effective at removing DOC.     

聚氯乙烯离心母液的处理及回用

采用接触氧化法处理悬浮法生产聚氯乙烯产生的离心母液,工程实践表明:离心母液经接触氧化工艺处理后COD去除率>85%,出水COD<50mg/L;再经过砂滤、臭氧氧化、活性炭过滤等深度处理后,出水COD、pH、浊度、电导率均达到回用要求。深度处理费用低于自来水基本水费(天津),也低于用自来水制备脱盐水的费用。     

Comparison of disinfection byproduct formation from chlorine and alternative disinfectants

Seven diverse natural waters were collected and treated in the laboratory under five oxidation scenarios (chlorine, chloramine, both with and without preozonation, and chlorine dioxide). The impact of these disinfectants on the formation of disinfection byproducts was investigated. Results showed that preozonation decreased the formation of trihalomethanes (THMs), haloacetic acids (HAAs) and total organic halogen (TOX) for most waters during postchlorination. A net increase in THMs, HAAs and TOX was observed for a water of low humic content. Either decreases or increases were observed in dihaloacetic acids and unknown TOX (UTOX) as a result of preozonation when used with chloramination. Chloramines and chlorine dioxide produced a higher percentage of UTOX than free chlorine. They also formed more iodoform and total organic iodine (TOI) than free chlorine in the presence of iodide. Free chlorine produced a much higher level of total organic chlorine (TOCl) and bromine (TOBr) than chloramines and chlorine dioxide in the presence of bromide.     

The formation of halogen-specific TOX from chlorination and chloramination of natural organic matter isolates

The formation of disinfection by-products (DBPs) is a public health concern. An important way to evaluate the presence of DBPs is in terms of the total organic halogen (TOX), which can be further specified into total organic chlorine (TOCl), bromine (TOBr), and iodine (TOI). The formation and distribution of halogen-specific TOX during chlorination and chloramination of natural organic matter (NOM) isolates in the presence of bromide and iodide ions were studied. As expected, chloramination produced significantly less TOX than chlorination. TOCl was the dominant species formed in both chlorination and chloramination. TOI was always produced in chloramination, but not in chlorination when high chlorine dose was used, due to the limited presence of HOI in chlorination as a result of the oxidation of iodide to iodate in the presence of excess chlorine. The formation of TOI during chloramination increased as the initial iodide ion concentration increased, with a maximum of ∼60% of the initial iodide ion becoming incorporated into NOM. Iodine incorporation in NOM was consistently higher than bromine incorporation, demonstrating that the competitive reactions between bromine and iodine species in chloramination favoured the formation of HOI and thus TOI, rather than TOBr. Correlations between the aromatic character of the NOM isolates (SUVA₂₅₄ and % aromatic C) and the concentrations of overall TOX and halogen-specific TOX in chloramination were observed. This indicates that the aromatic moieties in NOM, as indicated by SUVA₂₅₄ and % aromatic C, play an important role in the formation of overall TOX and halogen-specific TOX in chloramination. THMs comprised only a fraction of TOX, up to 7% in chloramination and up to 47% in chlorination. Although chloramine produces less TOX than chlorine, it formed proportionally more non-THM DBPs than chlorine. These non-THM DBPs are mostly unknown, corresponding to unknown health risks. Considering the higher potential for formation of iodinated DBPs and unknown DBPs associated with the use of chloramine, water utilities need to carefully balance the risks and benefits of using chloramine as an alternative disinfectant to chlorine in order to satisfy guideline values for THMs.     

Heterotrophic activity compromises autotrophic nitrogen removal in membrane-aerated biofilms: results of a modeling study

A 1-d multi-population biofilm model was constructed to study the effect of heterotrophic activity on completely autotrophic ammonium (NH4+) removal in membrane-aerated (counter-diffusion) versus conventional biofilm systems (co-diffusion). Growth of heterotrophic bacteria (HB) was supported either solely by biomass decay products or by organic carbon (as chemical oxygen demand (COD)) in the influent. Three scenarios were considered: influence of HB growing on biomass decay products on steady-state performance (total nitrogen (TN) removal efficiency); influence of the influent COD/N ratio on steady-state performance (supplying COD in the influent); and impact of dynamic changes in the influent COD/N ratio on TN removal efficiency. The results revealed that the TN removal efficiency in the counter-diffusion biofilm was significantly different when HB were included in the simulations at NH4+ surface loads of LNH4>2.7 g - N m(-2) d(-1). Influent COD significantly altered the microbial community composition in the counter-diffusion biofilm and anaerobic NH4+ oxidation could not be sustained at COD/N>2. The co-diffusion system, however, was less affected and more than 50% of the TN removal originated from anaerobic NH4+ oxidation at those ratios. Perturbation experiments showed that step increases to influent COD/N ratios of 2 or higher over a period of 50 d or longer caused a loss of anaerobic NH4+ oxidation capacity which could not be regained within a reasonable time frame (>1000 d) in the counter-diffusion system. In contrast, simulating a 1-d sloughing event only caused a disturbance of 200 d although a maximum biofilm loss of 90-95% occurred. These results clearly indicate the importance of heterotrophic activity in autotrophic N removal biofilms, especially in counter-diffusion systems where they may compromise N removal capacity.     

Fenton法处理垃圾渗滤液

介绍了Fenton法处理垃圾渗滤液的中型试验,其中Fenton氧化在连续搅拌反应器（CSTR）中进行。试验表明,当双氧水与亚铁盐的总投加比一定（H2O2／Fe^2 =3.0)时,COD的去除率随双氧水投加量的增加而增加,但与双氧水在两个氧化槽的投加比例无关。当双氧水的总投加量为0.1mol/L时,COD的去除率可达67．5％,这一结果同样适用于其他垃圾填埋场的晚期渗滤液处理。     

Olive mill wastewater treatment by anodic oxidation with parallel plate electrodes

Olive mill wastewater is characterized by very high chemical oxygen demand (COD) values and contains high concentrations of polyphenols that inhibit the activity of micro-organisms during biological oxidations. In this paper, the applicability of electrochemical oxidation of a real olive-mill wastewater was studied by performing galvanostatic electrolysis using parallel plate electrodes. A mixed titanium and ruthenium oxide (Ti/TiRuO2) was used as anode and stainless steel as cathode. The effect of chloride concentration and applied current on the removal of COD, aromatic content and colour was investigated. The experimental results showed that an effective electrochemical oxidation was achieved in which the wastewater was decolourised and the COD and aromatic content completely eliminated. In particular, the mineralisation took place by indirect oxidation, mediated by active chlorine, and the COD removal rate was enhanced by the addition of 5 g L(-1) of NaCl to the wastewater and by increasing the applied current.     

The microcoulometric determination of extractable organic halogen in surface water; Application to surface waters of The Netherlands

In this paper an analytical method is described for the microcoulometric determination of extractable organic halogen, especially chlorine, in surface waters and sediments. The minimum detectable amounts of chlorine are respectivelly 1.0 μg/l (ppb) in water and 0.5 mg/kg (ppm) in sediments. The results of a monitoring program in the river Rhine and several Dutch surface waters with respect to this parameter are presented. The results cover the period January 1973 to December 1975.In 1973, 1974 and 1975 the average daily loads of organic halogen calculated as chlorine in the river Rhine at Lobith were 3300, 3410 and 2050 kg, respectively.The parameter “Extractable Organic Chlorine” (EOCl) is suggested as a useful general indicator for chemical pollution in surface waters and in effluents from industrial plants.     

Etude physicochimique de la chloration de l'eau de mer artificielle contenant de l'azote ammoniacal

Chlorine added to ammonia-free sea-water gives rise to a fast and quantitative oxidation of bromide to hypobromite and hypobromous acid. However as ammonia nitrogen levels commonly found in coastal and estuarine sea-water are sufficiently high and thus not negligible compared to the chlorine dose introduced formation of monochloramine to compete with oxidation of bromine leading to bromamines. The relative importance of these two reactional pathways is estimated considering both bromine determination and study of the electron absorption spectra of chlorinated seawater. In order to avoid substitution reactions taking place in the presence of organic compounds, preliminary experiments have been carried out in artificial and u.v. photo-oxidized sea-water.The nature of the species formed depends on the molar ratio added chlorine vs ammonia-nitrogen concentration of seawater. With Cl/N larger than 1.5, only bromide derivatives are obtained: dibromamine, tribromamine and bromine(I) (HBrO + BrO⁻). Cl/N smaller than 1.5 leads to a mixture of monochloramine, dibromamine and some monobromamine: monochloramine clearly predominates when ammonium concentrations reach higher values. Stoichiometry of ammonia to nitrogen oxidation by chlorine explains this ratio of 1.5 and a strong decrease of the total oxidant concentration is observed under these conditions. Bromamines decompose within the following 30–60 min; only stable compounds remain: either bromine(I) or monochloramine according to Cl/N values. A similar behaviour is observed in natural seawater previously doped with ammonia as to the nature of the products formed for a given Cl/N ratio; however, bromamines decompose more rapidly due to bromination of organic components.     

Application of ferrous hydrogen peroxide for treatment of DSD-acid manufacturing process wastewater

A pretreatment method for the biological treatment of wastewater from 4,4'-diaminostilbene-2,2'-disulfonic acid (DSD-acid) manufacturing processes, a refractory dye intermediate wastewater, based on combined ferrous hydrogen peroxide oxidation and coagulation-flocculation, was developed. When the wastewater was treated with ferrous hydrogen peroxide oxidation ([Fe2+] = 2.7 mmol/L, [H2O2] = 0.21 mol/L) after a flocculation using an organic flocculant TS-1 at a dosage of 3 g/L, the overall COD and color removals were 64 and 62%, respectively. BOD5/COD value of the effluent was 0.3. Ferrous hydrogen peroxide oxidation treatment can reduce the solubility of organic molecules with sulfonic group and increase the efficiency of coagulation treatment. The COD and color removals were both more than 90% when FeCl3 was used as the coagulation (dosages of two-step coagulation were 0.031 and 0.012 mol/L respectively) after a ferrous hydrogen peroxide oxidation pretreatment at a H2O2 dosage of 0.06 mol/L.     

Formation of halogenated organic byproducts during medium-pressure UV and chlorine coexposure of model compounds, NOM and bromide

When chlorine is applied before or during UV disinfection of bromide-containing water, interactions between chlorine, bromide and UV light are inevitable. Formation of halogenated organic byproducts was studied during medium-pressure UV (MPUV) and chlorine coexposure of phenol, nitrobenzene and benzoic acid and maleic acid, chosen to represent electron-donating aromatics, electron-withdrawing aromatics, and aliphatic structures in natural organic matter (NOM), respectively. All were evaluated in the presence and absence of bromide. MPUV and chlorine coexposure of phenol produced less total organic halogen (TOX, a collective parameter for halogenated organic byproducts) than chlorination in the dark, and more haloacetic acids instead of halophenols. Increases in TOX were found in the coexposure of nitrobenzene and benzoic acid, but maleic acid was rather inert during coexposure. The presence of bromide increased the formation of brominated TOX but did not significantly affect total TOX formation, in spite of the fact that it reduced hydroxyl radical levels. MPUV and chlorine coexposure of NOM gave a higher differential UV absorbance of NOM and a larger shift to lower molecular weight compounds than chlorination in the dark. However, TOX formation with NOM remained similar to that observed from dark chlorination.     

An advanced oxidation process for DBP control

Small water utilities often have difficulty operating complicated treatment processes. The advanced oxidation process investigated here is simple, involving only a pump to add hydrogen peroxide and a power supply for the ultraviolet lamps, and the process does not produce any solid residuals. The results of these studies show that a photon-flux-driven pseudo-first-order model (known as the Prengle-Shimoda rate model) could be used to predict the destruction of total organic carbon, dissolved organic halogen, and dissolved organic halogen precursors.     

Electroflottation et desinfection simultanee d'eaux residuaires urbainesSimultaneous electroflotation and disinfection of sewage

This reports presents the results of a simultaneous electroflotation and disinfection sewage treatment, after chemical coagulation and flocculation and in the presence of chloride ions at various concentrations. Theoretical studies had shown that anodic oxidation of chloride ions gives hyperchlorites (for pH 7.5) together with (if sufficient potential is provided) oxygen. A dynamic study was thus achieved. It appeared that for a given chloride concentration the chlorine production linearly increases with the current density and depends on the organic load (COD) and oxidation potential of the effluent (Figs 6, 7 and 8). The performances of the process were studied in the continuous mode on a small pilot plant, after treatment of the effluent with ferric chloride and an organic polymer (Fig. 2). In all experiments current density and chloride concentration were raised (respectively 100, 200, 300 A m^?2 and from 300 to 3000 mg l^?1). The results obtained showed that solid-liquid separation was improved over static clarification for 2 h (Table 3) and the disinfection efficiency was equal or better than that obtained with gaseous chlorine (Table 4, Fig. 9). For example at a 900 mg l^?1 chloride concentration the three current density used give treated water containing less than 10³/100 ml total coliforms (initial concentration 4.7 · 10⁷/100 ml). These results have direct applications to the design of electroflotation units where a better plug flow should be sought. Moreover this process produces highly concentrated sludges. The utilization of ATP (Adenosine Triphosphate) as an indicator of the viability of a biomass showed that the process is applicable to activated sludges with recycling. The experimental conditions required for this application are still uncertain and require further study.     

Improving anaerobic sequencing batch reactor performance by modifying operational parameters.

A lab-scale anaerobic sequencing batch reactor (ASBR) that had operated with glucose at an organic loading rate of 2.1 kg COD m(-3) d(-1) was stressed with an organic loading rate of 3.2 kg COD m(-3) (-1). Five different combinations of influent concentration, total cycle time, and fill time to cycle time ratio were examined. No external pH control was used. In all cases, acetate and propionate were the main constituents of the effluent. Larger fill time to cycle time ratios and lower initial substrate concentrations resulted in improved performance suggesting that ASBR operation may be improved by changing operational parameters.     

Simultaneous removal of organic matter and nitrogen compounds by an aerobic/anoxic membrane biofilm reactor

The hydrogen-based membrane biofilm reactor (MBfR) has been well studied and applied for denitrification of nitrate-containing water and wastewater. Adding an oxygen-based MBfR allows total-nitrogen removal when the input nitrogen is ammonium. However, most wastewaters also contain a significant concentration or organic material, measured as chemical oxygen demand (COD). This study describes experiments to investigate the removal of organic and nitrogenous compounds in the combined Aerobic/Anoxic MBfR, in which an Aerobic MBfR (Aer MBfR) precedes an Anoxic MBfR (An MBfR). The experiments demonstrate that the Aer/An MBfR combination accomplished COD oxidation and nitrogen removal for a total oxygen demand flux (i.e., from COD and NH(4) oxidations) in the range of 1.2-7.2gO(2)/m(2)-d for 4.5psi (0.3atm) oxygen pressure to the Aer MBfR, but was overloaded and did not accomplish nitrification for the total oxygen demand load higher than 14gO(2)/m(2)-d. Total-nitrogen removal was controlled by nitrification in the Aer MBfR, because the An MBfR denitrified all NO(3)(-) provided to it by the Aer MBfR. The overload of total oxygen demand did not affect COD oxidation in the Aer MBfR, but caused a small increase of COD in the An MBfR due to net release of soluble microbial products (SMP).