Integrating water temperature in chlorine decay modelling: a case study

Temperature is one of the factors that most influences chlorine decay rates in drinking water systems. The current paper assesses and demonstrates the importance of using a temperature dependent chlorine bulk decay model for the accurate prediction of disinfectant residuals in water supply systems. Chlorine concentration in a water transmission system was modelled for two seasons using a temperature-dependent bulk decay model at a constant and variable temperature. Results show that water temperature can vary within the system and that the accurate prediction of residuals may additionally require the incorporation of a water temperature model in the simulators. In this case study such approach was developed innovatively by establishing a water-age-dependent temperature function.     

MD镇供水管网余氯衰减模拟

采用EPANET2建立了MD镇的管网水质模型,通过EPANET2的水质模拟分析与实际数据的对比,分析可能存在的问题。对可能存在的问题进行现场调查,进而对节点需水量和管壁衰减系数Kw进行调整,从而使模型中的模拟余氯与实测余氯相符。     

A model for chlorine concentration decay in pipes

A model that accounts for transport in the axial direction by convection and in the radial direction by diffusion and that incorporates first order decay kinetics has been developed to predict the chlorine concentration in a pipe in a distribution system. A generalized expression for chlorine consumption at the pipe wall is used to solve the governing equation and to determine the average chlorine concentration at any location in the pipe. Three non-dimensional parameters are used to determine the concentration and a methodology to determine them in pipe networks is proposed. The range of values of these dimensionless parameters where wall consumption is significant are determined. The methodology is applied to field measurements of chlorine concentration in a distribution network.     

A comprehensive bulk chlorine decay model for simulating residuals in water distribution systems

Chlorine decay models provide efficient ways to develop disinfection strategies for water distribution systems, provided they account separately for bulk and wall decay, and accurately describe decay with a single set of coefficients. The augmented two-reactant (2RA) model is shown to be the simplest model to accurately describe effects of rechlorination dose/timing on bulk chlorine decay, in combination with effects of initial concentration and temperature over long periods. The two-reactant (2R) and variable reaction-coefficient (VRC) models provided predictions of comparable accuracy under higher and successive rechlorination doses at constant temperature. However, the 2RA model provides a more general basis for strategy development, as the VRC model cannot describe the effect of temperature variation. The minimal data-set required for 2RA calibration was similar for all cases considered. The 2RA model is readily applied by incorporation into system modelling software such as the multi-species extension (MSX) to EPANET software.     

A new approximate solution for chlorine concentration decay in pipes

Biswas et al. (1993. A model for chlorine concentration decay in pipes. Water Res. 27(12), 1715-1724) presented an analytical solution of a two-dimensional (2-D) steady-state chlorine transport equation in a pipe under the turbulent condition and employed fractional error function and regression technique to develop an approximate solution. However, their approximate solution may not give a good result if the wall decay parameter is large. This paper provides a more accurate approximate solution of the 2-D steady-state chlorine transport equation under the turbulent condition. This new approximate solution has advantages of easy evaluation and good accuracy when compared with the approximate solution given by Biswas et al. (1993). In addition, this paper also develops a methodology that combines simulated annealing (SA) with this new approximate solution to determine the wall decay parameter. Two cases are chosen to demonstrate the application of the present approximate solution and methodology. The first case is to use this new approximate solution in simulating chlorine decay in pipes with the experiment-observed data given by Rossman (2006. The effect of advanced treatment on chlorine decay in metallic pipes. Water Res. 40(13), 2493-2502), while the second case presents the determination of the wall consumption at the end of the pipe network.     

分光光度法测水中余氯

介绍了用双硫腙分光光度法测定水中余氯的新方法，阐述了其测定试验过程，根据试验结果显示，其结论符合国家标准，表明该方法可用于自来水等样品中余氯含量的测定，结果比较准确。     

对氨基二甲苯胺分光光度法测定水中余氯

建立了对氨基二甲苯胺分光光度法测定水中余氯的新方法。利用氯气在一定条件下能氧化对氨基二甲苯胺使其成为红色的氧化态形式 ,可以定量测定氯 ,实验条件如下 :最大吸收波长为5 2 0 nm ,p H控制在 2 .5～ 4.0之间 ,缓冲溶液用量为 2 ml,显色液体积为 3ml。氯浓度在 0 .1～2 .0 mg/L范围服从比尔定律。检测限 c L D为 0 .0 2 mg/L,水中常见的离子不干扰测定。该法用于自来水等样品中余氯含量的测定 ,加标回收率在 98%～ 1 0 4 %之间 ,结果准确可靠。     

Comparison of three methods for measuring residual chlorine

Three EPA-approved residual chlorine detection methods were compared using standard solutions and water collected from the Savannah River which is used to cool reactors at the Savannah River Site (SRS) near Aiken, S.C. The testing was part of an experimental program to develop baseline data for the design of a proposed cooling tower for the K-reactor at the SRS. A series of total residual chlorine (TRC) measurements made simultaneously by three methods revealed that for the river water samples, the DPD method (Hach DR-100 kit) and the amperometric titration method produced statistically similar results while an ion-selective electrode method, standardized according to the manufacturer's instructions, provided significantly lower values. The DPD method (utilizing a Hach DR-100 kit) was the recommended method for future monitoring of the water evaluated because this method is simple, provides quick results, measures both total residual chlorine (TRC) and free residual chlorine (FRC) and is equally suitable for measurements in the field and laboratory.     

Sampling design for water distribution network chlorine decay calibration

This paper provides a novel approach to determining optimal sampling locations for chlorine decay model calibration. Three questions are investigated: (1) What is the minimum number of chlorine sample locations needed? (2) How many combinations of sampling locations are available? (3) What is the optimal location combination? To answer the first two questions, the mathematical expressions of the chlorine concentrations between any two sampling locations are developed and sampling point relationship matrices are generated, then a mixed integer programming (MIP) algorithm is developed. Once obtained, the solutions to the first two questions are used to calculate the chlorine decay wall reaction coefficients and sensitivity matrix of chlorine concentration to wall reaction coefficients; then, sampling location combinations achieved in the second question are sorted using a D-optimality algorithm. The model frame is demonstrated in a case study.     

A suitable model of combined effects of temperature and initial condition on chlorine bulk decay in water distribution systems

Maintaining a chlorine residual is a major disinfection goal in many water distribution systems. A suitable general model of chlorine decay in the transported bulk water is an essential component for efficiently modelling chlorine concentration in distribution systems. The two-reactant model meets basic suitability criteria, including accurate prediction of chlorine residual over hundreds of hours, commencing with chlorine concentration 0-4 mg/L. This model was augmented with an equation that increases the decay coefficients with temperature according to Arrhenius theory. The augmented model was calibrated against decay-test data sets to obtain a single invariant set of parameters for each water. Model estimates of chlorine residuals over time closely matched decay-test data, over the usual operating ranges of initial chlorine concentration (1-4 mg/L) and temperature (3.5-28 °C). When the augmented model was fitted to partial data sets, it also predicted the data reserved for validation very well, suggesting that this model can accurately predict the combined effect of initial chlorine concentration and temperature on chlorine bulk decay in distribution systems, using a single set of invariant parameters for a given source water.     

The effect of advanced treatment on chlorine decay in metallic pipes

Experiments were run to measure what effect advanced treatment might have on the kinetics of chlorine and chloramine decay in metallic pipes that comprise many drinking water distribution systems. A recirculating loop of 6-in diameter unlined ductile iron pipe was used to simulate turbulent flow conditions in a pipe with significant corrosion and tubercle buildup. Conventionally treated test water was subjected to either ozonation, carbon adsorption (GAC), reverse osmosis (RO) or no further treatment before being chlorinated and introduced into the pipeline simulator. Results showed that overall chlorine decay in the simulator was consistently dominated by wall reactions whose first-order rate constants were an order of magnitude higher than those for the bulk water. With free chlorine, the wall rate constants for ozonated and GAC-treated water were about twice those of conventional or RO-treated water. This behavior is believed due to the effect that changes in the organic content of water have on its ability to complex iron and the effect that changes in water conductivity have on pipe wall corrosion. Tests run with chloraminated water showed no statistically significant effect of treatment type and had wall rate constants that were only 40 to 70% as high as those using free chlorine.     

Inactivation of Naegleria gruberi cysts by chlorine dioxide

Investigations were carried out to determine the kinetics of chlorine dioxide inactivation of Naegleria gruberi cysts and the influence of pH from 5 to 9, temperature from 5 to 30°C, cyst age from 3 to 12 days, and cyst clumping. Inactivation was characterized by an initial concave downward shoulder followed by an essentially linear portion but the process obeyed Watson's Law. At 25°C and pH 7 the mean concentration time product for 99% inactivation was 5.5 mg·min l⁻¹. These products varied inversely with temperature and pH.     

Decay of disinfectant residual in overland flow

Chlorine is a widely used disinfectant that can have impact on receiving water bodies. Both chemical and non-chemical methods are available to reduce concentrations to acceptable levels after chlorinated water is discharged from hydrants. This paper reports on tests of chlorine decay both in the laboratory and the field, and discusses other factors such as chlorine demand of the receiving water body and dilution. A protocol is presented to help water utility personnel decide if chemical dechlorination is recommended during hydrant discharges.     

PSO-SVM与BP神经网络组合预测供水系统余氯的方法

针对余氯量在供水系统内非线性变化的特性,建立了PSO-SVM与BP神经网络组合模型对管网末端余氯进行预测分析。该模型通过粒子群优化算法(PSO),对SVM的特性参数进行优化;采用BP神经网络对模型进行残差修正。通过对单一的BP模型和SVM模型、组合模型的预测精度进行分析。结果表明:组合模型预测比BP和SVM单一预测均方误差分别降低了62.30%、75.29%,平均相对误差降低了55.03%、54.27%。综上所述,该模型具有强大的非线性拟合能力,预测精度高,运行稳定性强,对供水企业控制余氯的投加量和设置二次加氯点有一定的指导作用。     

Catalysis of copper corrosion products on chlorine decay and HAA formation in simulated distribution systems

This study investigated the effect of copper corrosion products, including Cu(II), Cu₂O, CuO and Cu₂(OH)₂CO₃, on chlorine degradation, HAA formation, and HAA speciation under controlled experimental conditions. Chlorine decay and HAA formation were significantly enhanced in the presence of copper with the extent of copper catalysis being affected by the solution pH and the concentration of copper corrosion products. Accelerated chlorine decay and increased HAA formation were observed at pH 8.6 in the presence of 1.0 mg/L Cu(II) compared with that observed at pH 6.6 and pH 7.6. Further investigation of chlorine decay in the presence of both Suwannee River NOM and Cu(II) indicated that an increased reactivity of NOM with dissolved and/or solid surface-associated Cu(II), rather than chlorine auto-decomposition, was a primary reason for the observed rapid chlorine decay. Copper corrosion solids [Cu₂O, CuO, Cu₂(OH)₂CO₃] exhibited catalytic effects on both chlorine decay and HAA formation. Contrary to the results observed when in the absence of copper corrosion products, DCAA formation was consistently predominant over other HAA species in the presence of copper corrosion products, especially at neutral and high pH. This study improves the understanding for water utilities and households regarding chlorine residuals and HAA concentrations in distribution systems, in particular once the water reaches domestic plumbing where copper is widely used.     

The different reaction mechanisms by which chlorine and chlorine dioxide react with polycyclic aromatic hydrocarbons (PAH) in water

The removal of PAH from surface water by disinfectants like chlorine or chlorine dioxide is important where contamination by these compounds is concerned and no other water treatment processes are available. Our particular interest in these reactions arise from the fact that PAH can be used as an excellent model for the investigation of the different mechanisms by which the two oxidants react with aquatic organics. The vast differences between the rates of Cl₂ and ClO₂ reactions with various PAH, as well as the physical and chemical factors influencing those reactions indicate that chlorine reacts with PAH by several possible mechanisms, e.g. addition, substitution and oxidation. Chlorine dioxide on the other hand reacts mainly as a pure oxidant and a one-electron acceptor. As a consequence, chlorine dioxide reacts much more specifically with those PAH that undergo facile oxidation. Therefore, some PAH that react quite easily with Cl₂, do not react at all with ClO₂, while other PAH react with ClO₂ much more rapidly than with Cl₂. The widespread and highly carcinogenic benzo(a)pyrene and benzo(a)anthracene for example react with ClO₂ much faster than with Cl₂.     

枯水期出厂水余氯突降原因与对策

针对江门市出厂水在枯水期出现余氯突降的现象,分析了出厂水余氯异常时出厂水及原水水质的变化情况、原水发生微污染时与河流潮汐的关系、原水氨氮和耗氧量的关系、原水氨氮和出厂水余氯的关系。结果表明,出厂水余氯出现突降是由于原水受到微污染造成的;氨氮、耗氧量以及河床水位可以作为原水微污染的预警指标,操作简单、有效;当预测到原水出现微污染时,采取加大和调整前后加氯量的方式,可解决由于原水微污染而引起的出厂水余氯突降的问题。     

Using Bayesian statistics to estimate the coefficients of a two- component second-order chlorine bulk decay model for a water distribution system

Most chlorine decay models for the bulk phase in a water distribution system consider only chlorine concentration and time. Clark [1998. Chlorine demand and trihalomethane formation kinetics: a second-order model. J. Environ. Eng. 124(1), 16-24] first proposed a two-component second-order chlorine decay model based on the concept of competing reacting substances. A corrected mathematical formulation is developed and, because the recent findings suggested that not all natural organic matter (NOM) is involved in the chlorine decay process, an additional parameter is introduced. A parameter assignment method employing Bayesian statistical analysis incorporating Monte Carlo Markov chain (MCMC) with Gibbs sampling to make inferences, is employed in the estimation of model parameters. Three parameters are estimated for the model, namely the ratio of chlorine to TOC, the chlorine reaction rate, and a fraction factor of TOC which represents the true amount of TOC involved in chlorine decay process. Water samples taken from Goderich in the summer of 2005, are used for estimating the parameters.     

Disinfection of advanced wastewater treatment effluent by chlorine, chlorine dioxide and ozone: Experiments using seeded poliovirus

Chlorine, chlorine dioxide and ozone were tested as chemical disinfectants against seeded poliovirus and naturally-occurring fecal coliform organisms in wastewater effluent that had received secondary treatment followed by bench scale advanced wastewater treatment (AWT). The AWT sequence consisted of chemical treatment with lime or alum followed by mixed media filtration. The resulting effluent had low suspended solids concentrations but chemical oxygen demand and nitrogen concentrations only slightly lower than those of secondary effluent. Lime treatment produced greater reductions than alum treatment in virus numbers, but not in fecal coliform organisms.

With both chlorine and chlorine dioxide, in order to reduce seeded poliovirus to less than detectable levels, it was necessary to use doses comparable to those required to disinfect secondary effluent. The required contact times of 30–60 min were also comparable. Utilized ozone doses of 2–4 mg l⁻¹ were required to reduce seeded poliovirus to less than detectable levels in AWT effluent. Naturally-occurring fecal coliform organisms were unaffected at these ozone doses, but were inactivated at higher doses. Because they were more resistant than seeded poliovirus to ozone, fecal coliform organisms show promise as indicators for ozone disinfection.     

Sequential inactivation of Cryptosporidium parvum using ozone and chlorine.

Inactivation of bovine-derived C. parvum oocysts was studied at bench-scale in oxidant demand free 0.05 M phosphate buffer using free chlorine alone or ozone followed by free chlorine at temperatures of 1°C, 10°C and 22°C at pH 6. Animal infectivity using neonatal CD-1 mice was used for evaluation of oocyst viability after treatment. Kinetic models based on the linear Chick–Watson model were developed for free chlorine inactivation and ozone/free chlorine sequential inactivation for 0.4 or 1.6 log-units of ozone primary kill. At 22°C, ozone pre-treatment increased the efficacy of free chlorine for about 4–6 times depending on the level of ozone primary kills. Gross kills of the ozone/free chlorine sequential inactivation were a function of ozone primary kills and increased linearly with the free chlorine C_avgt (arithmetic average of the initial and final residual×contact time) product. Temperature was critical for both single and sequential inactivation, and the efficacy of free chlorine after 1.6 log-units of ozone primary inactivation decreased by a factor of 1.8 for every 10°C temperature decrease. Given an ozone primary kill of 1.6 log-units, the free chlorine C_avgt products required for a gross kill of 3.0 log-units were 1000, 2000 and 3300 mg min/L for 22°C, 10°C and 1°C, respectively.