Bulk Chlorine Research Articles

The mixed-order chlorine decay model with an analytical solution and corresponding trihalomethane generation model in drinking water

Ensuring effective drinking water disinfection, remaining a certain amount of residual chlorine, and controlling disinfection by-product formation were very important for guarantying water quality safety and protecting public health; thus, the chlorine decay model and corresponding disinfection by-product formation model were necessary. This paper proposed a mixed-order chlorine bulk decay model (two parameters) based on Taylor's formula and derived its analytical solution. The accuracy of the mixed-order model was evaluated by comparing it with the nth-order model. To optimize the model and reduce the number of parameters required to be calibrated, the relationship of parameters with temperature, initial chlorine concentration, TOC and inorganic substance (ammonia nitrogen and iodide ion) was explored. The result proved that one of the parameters could be regarded as temperature dependent only. Meanwhile, the temperature equation of the model parameters was established by the Arrhenius formula. Subsequently, this paper selected trihalomethane as the target and study the linear relationship between chlorine consumption and trihalomethane formation. The results indicated that the liner slope had little correlation with initial chlorine concentration and temperature. On this basis, the corresponding trihalomethane model was built and its performance was proven to be good. The modeling developed in this work could be applied to drinking water distribution systems for residual chlorine and trihalomethane prediction, and provided a reference for the decision involving water quality.

Effects of storage conditions on superoxidised water

Superoxidised water (SOW) in the food industry has several advantages over traditional chemical disinfectants. SOW is non-toxic and environmentally friendly and does not leave any harmful by-products. In addition, SOW is easy to use and can be applied to various food surfaces. SOW has been used to avoid the food industry's biological pollution caused by food-borne bacteria pathogens with recognized as a short producing time and evident in the sterilization process, SOW is highly recommended for its eco-friendly ability. Chlorine-containing solutions such as SOW are used for broad disinfection purposes, including in the food industry. Still, their effectiveness and stabilities often need to be investigated as residues such as chlorine in SOW are not stable. The efficacy of SOW can be easily affected by several factors, including pH, temperature, and organic matter content. In this study, the two different storage conditions influenced by the light exploration were used to investigate the light condition that directly impacts the chlorine level in SOW. Light intensity plays an important role in determining chlorine loss from SOW. Chlorine dissipation rates in the light condition are higher than in the dark condition. With the initial 40+0.00 mg/L of chlorine, the chlorine level was decreased as plastic bottle/light > glass bottle/light > plastic bottle/without light> glass bottle/without light. They show that the change in chlorine level is significantly influenced by the type of bottle and the environmental condition, such as light intensity, in this study. The results obtained in this study validate the practice of SOW’s storage condition to slow down chlorine's bulk decay when applied in various industries, such as the food industry.

Depth Distribution of Chlorine at Gale Crater, Mars, as Derived From the DAN and APXS Experiments Onboard the Curiosity Rover

AbstractThe subsurface chlorine depth distribution at Gale crater has been studied using measurements from the Alpha Particle X‐ray Spectrometer (APXS) and Dynamic Albedo of Neutrons (DAN) instruments onboard NASA's Curiosity Mars rover. These measurements have been acquired at or near ∼30 drill holes made by Curiosity along its 30 km drive. APXS measured a ∼15 micron surface layer of bedrock and shallow depth of ∼5 cm of drill tailings. DAN is sensitive to the bulk (∼50 cm depth) chlorine abundance and that of other neutron absorbing elements. Joint analysis of APXS and DAN data shows that the chlorine distribution at Gale crater consists of two components: surficial chlorine with concentrations >1 wt.%, possibly controlled by aeolian deposition of Cl‐rich dust and surface alteration, and subsurface chlorine with concentrations <1 wt.%, likely a result of groundwater activity in the past.

Full-scale determination of pipe wall and bulk chlorine degradation coefficients for different pipe categories

Abstract Having good information about parameters that impact water quality can improve the management of water distribution systems in the short-term (optimising disinfection) and the long-term (planning rehabilitation). Full-scale data on the degradation of the residual disinfectant for various pipe characteristics are difficult to obtain but necessary. As the most common disinfectant is chlorine, this paper aims to determine the most important pipe and/or hydraulic system characteristics in the chlorine degradation coefficients. Such characteristics were identified based on statistical analyses that relate them with range values of bulk and pipe wall degradation coefficients estimated in full-scale conditions in a real distribution system. The results showed that among pipe characteristics, the period of installation impacts significantly kw and kt. Results of kw for three different materials confirmed that residual chlorine degradation at the pipe walls for grey-cast iron, which is older and metallic, is much higher than that for ductile cast iron and PVC pipes. In older pipes, up to 97% of residual chlorine can be degraded at the pipe walls, while the role of bulk reactions can reach about 35% in newer pipes. The obtained information can be integrated to identify pipes for rehabilitation/renewal and locations for booster rechlorination.

Uncertainty analysis of water quality in water distribution system

Abstract Water quality simulation is affected by uncertain parameters such as pipe roughness coefficients, chlorine bulk decay coefficients, and chlorine wall decay coefficients, which are usually considered to be fuzzy variables. The minimum and maximum nodal chlorine concentrations and water ages at each α-cut level were obtained by the genetic algorithm (GA) based on EPANET hydraulic and water quality simulation toolkit. The fuzziness of nodal chlorine concentrations and water ages were measured using the fuzziness measure (FM) proposed in this paper. The method was applied to four networks to analyze the fuzziness of nodal chlorine concentrations and water ages. The results indicated that the distribution of nodal chlorine concentrations does not follow typical trapezoid distribution, while the distribution of nodal water ages follows typical trapezoid distribution. In addition, the chlorine concentration and water ages of nodes farther from the source are affected by uncertain parameters to a greater extent. The greater demands of nodes lead to less effects of uncertain parameters on chlorine concentration, and greater effects of uncertain parameters on water ages. This study would help in analyzing the fuzziness of hydraulic and water quality simulation results in WDS under uncertain conditions.

The Influence of Organic Matter Origin on the Chlorine Bulk Decay Coefficient in Reclaimed Water

Using reclaimed water has been increasing to manage water shortages arising due to climate change. Research has been conducted on reclaimed water production, but few studies have investigated the pipe network and supply of reclaimed water. Reclaimed water contains greater amounts of organic matter, nutrients, and ionic substances compared to tap water. Therefore, it is highly likely to cause problems, such as water pollution due to microbial propagation in pipes, and leakage due to pipe corrosion, which interfere with water supply system operations. This study investigated the residual chlorine decay characteristics of chlorine disinfectants applied to a control biofilm in reclaimed water pipe networks. The bulk decay coefficient was compared between reclaimed water and a humic acid solution, and the origin of organic matter was analyzed using fluorescence excitation-emission matrices. The experimental results show that residual chlorine was consumed because protein and amino acid-based organic matter reacted more rapidly with chlorine than natural organic matter, such as humic acid. Moreover, chlorine bulk decay occurred rapidly in reclaimed water when total organic carbon was 3 mg/L or higher. These results confirm that removing organic matter during reclaimed water treatment may affect the management of the pipe network system.

Mitigation of Cyanobacterial Harmful Algal Blooms (cHABs) and Cyanotoxins by Electrochemical Oxidation: From a Bench-Scale Study to Field Application

Cyanobacterial harmful algal blooms (cHABs) and the concurrent release of cyanotoxins have become an emerging threat to aquatic life and drinking water safety. It is challenging for conventional water treatment infrastructures to mitigate cHAB events that occur frequently and irregularly. This study developed an emergency-responsive electrochemical oxidation and filtration (EOF) process that enables the pump-and-treat of phytoplankton plumes and cyanotoxins. Fundamental studies indicate that the EOF process generated locally concentrated free chlorine (>16 times higher than the bulk chlorine concentration) at the porous Ti4O7 filter anode surface. Lab tests showed that cyanobacteria and the cyanotoxin microcystin-LR were inactivated and destroyed by free chlorine when passing through the porous anode. Additionally, the concentration of disinfection byproducts generated by EOF was five times less than chlorination to achieve the same level of treatment. A boat-mount full-scale EOF system was developed and deployed in Lake Neatahwanta impacted by cHAB. The system can effectively remove >50% of phytoplankton and >80% of the ambient cyanotoxins at a treatment capacity of 110 m3/day and energy consumption of 1.1 kWh/m3. Instant improvement of effluent water clarity was achieved.

Modeling of residual chlorine in a drinking water network in times of pandemic of the SARS-CoV-2 (COVID-19)

Due to the outbreak of the novel coronavirus disease there is a need for public water supply of the highest quality. Adequate levels of chlorine allow immediate elimination of harmful bacteria and viruses and provide a protective residual throughout the drinking water distribution network (DWDN). Therefore, a residual chlorine decay model was developed to predict chlorine levels in a real drinking water distribution network. The model allowed determining human exposure to drinking water with a deficit of residual chlorine, considering that it is currently necessary for the population to have clean water to combat coronavirus Covid 19. The chlorine bulk decay rates (kb) and the reaction constant of chlorine with the pipe wall (kw) were experimentally determined. Average kb and kw values of 3.7 d− 1 and 0.066 m d− 1 were obtained, respectively. The values of kb and kw were used in EPANET to simulate the chlorine concentrations in a DWDN. The residual chlorine concentrations simulated by the properly calibrated and validated model were notably close to the actual concentrations measured at different points of the DWDN. The results showed that maintaining a chlorine concentration of 0.87 mg L− 1 in the distribution tank, the residual chlorine values in the nodes complied with the Ecuadorian standard (0.3 mg L− 1); meanwhile, about 45% of the nodes did not comply with what is recommended by the WHO as a mechanism to combat the current pandemic (0.5 mg L− 1). This study demonstrated that residual chlorine modeling is a valuable tool for monitoring water quality in the distribution network, allowing to control residual chlorine levels in this pandemic season.

Bulk and pipe wall chlorine degradation kinetics in three water distribution systems

ABSTRACT This paper presents a methodology to estimate free residual chlorine concentrations (FRCC) in full-scale water distribution system (WDS) using different degradation kinetics according to pipe material, age and diameter. Intensive field sampling campaigns and laboratory-scale tests were carried out to estimate total and bulk volume FRCC in three WDS. Bulk kinetic constants were estimated for water temperatures typical of different seasons in the Quebec City area (Canada). With field-measured FRCC at all sampling sites and an estimation of travel times through the use of a hydraulic model, total, bulk and pipe wall kinetic constants were obtained with ranges of 10.2 to 130.4, 4.1 to 43.8 and 8.5 to 114.9 10−3/h, respectively. Pipe wall kinetics tend to dominate the total degradation process for older grey and ductile cast-iron pipes, followed by newer ductile iron pipes and then PVC and pre-stressed concrete pipes (mostly installed from 1990). The developed methodology and results will be useful to improve the prediction of FRCC through hydraulic and water quality modelling.

Simultaneous Hydraulic and Quality Model Calibration of a Real-World Water Distribution Network

Hydraulic and quality models are widely used in water distribution networks (WDNs) for assisting network analysis, design, and operation. In a calibrated model, the difference between the simulated and measured data reaches an acceptable error level. In this study, to calibrate the hydraulic and quality model of the network, the pressure and residual chlorine levels were measured initially during 2-h steps in the network. Furthermore, the bulk chlorine decay values were measured using the laboratory tests. Then, hydraulic and quality calibrations were carried out simultaneously using particle swarm optimization (PSO) as the optimization tool, Hazen-Williams roughness (CH−W) and fitting coefficients as the decision variables, and mean absolute percentage error (MAPE) as the objective function. According to the results, the PSO algorithm was highly accurate in determining the CH−W and could minimize the difference between the observed and simulated values.

Relationship between chlorine decay and temperature in the drinking water

The bulk chlorine decay rate in drinking water supply systems depend on many factors, including temperature. In this document, the method to determine the order of reaction of chlorine with water is reported, as well as the method to estimate Kb (Bulk reaction rate constant). Experiments were carried out to determine the bulk chlorine decay, for which a set of water samples to determine the free residual chlorine every hour were analyzed. Chlorine concentrations were graphed against time and adjusted appropriately to the developed model. The experimental results showed that the average value of the mass decomposition rate was 0.15 h−1. It was shown that temperature affects the variation of the reaction rate of chlorine with water, Kb increases as temperature increases. In this manuscript it is reported:•The method that allows determining the reaction kinetic order of chlorine with drinking water.•The method that can help residual chlorine modelers in the correct definition of the bulk reaction rate constant.•The effectiveness of the method for evaluating the decomposition of residual chlorine in drinking water distribution networks as a function of temperature.

A Mathematical Model for Variable Chlorine Decay Rates in Water Distribution Systems

A model for relating the time-dependent variable rate of reaction to the decay of chlorine residual in water is developed based on the initial chlorine dose, molar concentrations of reactants, and the rate constant itself. The mathematical model, while retaining its second order nature, simplifies the solution as the residual chlorine and aggregate parameters such as molar concentration of reactants can be estimated. The model is based on molar-averaged reaction rates involving arithmetic and harmonic means of reactants that eliminate the individual reaction rates that are difficult to determine. Part of the mathematical assumption used in the derivation of the equations using molar averaging is tested for its validity through theoretical as well as Monte Carlo simulation of the error term over wide ranges of assumed reaction rates and molar concentration of reactants. The second-order variation of the rate of reaction with respect to the initial chlorine concentration has been verified through experimental tests of bulk chlorine decay carried out at different chlorine doses.

The chlorine isotope composition of iron meteorites: Evidence for the Cl isotope composition of the solar nebula and implications for extensive devolatilization during planet formation

AbstractThe bulk chlorine concentrations and isotopic compositions of a suite of non‐carbonaceous (NC) and carbonaceous (CC) iron meteorites were measured using gas source mass spectrometry. The δ37Cl values of magmatic irons range from −7.2 to 18.0‰ versus standard mean ocean chloride and are unrelated to their chlorine concentrations, which range from 0.3 to 161 ppm. Nonmagmatic IAB irons are comparatively Cl‐rich containing >161 ppm with δ37Cl values ranging from −6.1 to −3.2‰. The anomalously high and low δ37Cl values are inconsistent with a terrestrial source, and as Cl contents in magmatic irons are largely consistent with derivation from a chondrite‐like silicate complement, we suggest that Cl is indigenous to iron meteorites. Two NC irons, Cape York and Gibeon, have high cooling rates with anomalously high δ37Cl values of 13.4 and 18.0‰. We interpret these high isotopic compositions to result from Cl degassing during the disruption of their parent bodies, consistent with their low volatile contents (Ga, Ge, Ag). As no relevant mechanisms in iron meteorite parent bodies are expected to decrease δ37Cl values, whereas volatilization is known to increase δ37Cl values by the preferential loss of light isotopes, we interpret the low isotope values of <−5‰ and down to −7.2‰ to most closely represent the primordial isotopic composition of Cl in the solar nebula. Similar conclusions have been derived from low δ37Cl values down to −6, and −3.8‰ measured in Martian and Vestan meteorites, respectively. These low δ37Cl values are in contrast to those of chondrites which average around 0‰ previously explained by the incorporation of isotopically heavy HCl clathrate into chondrite parent bodies. The poor retention of low δ37Cl values in many differentiated planetary materials suggest that extensive devolatilization occurred during planet formation, which can explain Earth's high δ37Cl value by the loss of approximately 60% of the initial Cl content.

Development of prediction models of chlorine bulk decay coefficient by rechlorination in water distribution network

Development of prediction models of chlorine bulk decay coefficient by rechlorination in water distribution network

NEW AROMATIC DINITRODERIVATIVES OF CHLORAL AS MONOMER FOR SYNTHESYS OF POLYESTER AND POLYHETERO-ARYLENE

The synthesis of aromatic dinitroderivatives of chloral effectively used in production of soluble, heat and fire resistant polyester and polyhetero arylenes using in the reaction of aromatic nucleophilic replacement was studied. The groups of new aromatic dinitroderivatives containing chloral as central groups between the phenyl nuclei: dichlorethelyne, carbonyl, acetylene and methylene groups were considered. The synthesis conditions were improved for polyester polyesterketones, polyesteretherketones, poliftalimides and polynaphtalamids without substantially affecting the thermal and solid characteristics achieved under relatively mild conditions using nucleophilic polynitro substitution. The search of new functional groups used in the condensation reactions, is an urgent task of polymer chemistry. Such groups must be determined by enough high reactivity of the monomers, without reducing their availability and without increasing their toxicity. It has decisive importance in the structure of initial monomers, which would be determined by the properties of polymers and the solubility of the target. In this aspect, dinitro compounds containing diphenyl, phthalimide and naftalimidnye cycles are presented their unique structures. It is known that improvement in meltability and solubility of the polymers without significant effect on the thermal and strength properties achieved by the introduction of these "carded" groups bulky substituents or phenyl phenoxide, flexible "bridge" fragments and introduced into the aromatic nuclei of the starting compounds bulk chlorine atoms. As part of this review it was made an attempt to describe methods of synthesis and properties of aromatic dinitropro- derivatives containing combinations of bulky substituents and flexible "bridged" groups using as initial compounds the simplest derivatives of chloral. The mostly known polyimides and polyetherimides prepared by reacting dianhydrides of aromatic tetracarboxylic acids with aromatic diamines with two-staged process where the first stage, a poly (o-carboxy) imides, and the second, due to thermal or catalytic imidization of polyamides with low solubility in organic solvents. It should be noted that the second stage -thermal or catalytic imidization not always results in a totally cycling polyamides that reduces the possibility of a relatively high molecular weight of polymers. At using aromatic dinitro- compounds containing a phthalimide and naftalimide cycles as comonomers bis-phenols, the problem of the extent of cyclization is absent. It was noted that an important determinant of obtaining high molecular weight of polymers is using nucleophilic polinitro-substitution in a process flow on the first stage under relatively mild conditions in a medium of DMSO or DMSO / toluene at 70 °C for 2 h in a completely dry environment. The review deals with some aspects of activation mechanism of nitro groups in nucleophilic polynitro-substitution. The processes of synthesis of condensation monomers of dinitro-derivatives using chloral were considered in detail. The methods of preparation and some properties of aromatic dinitroarilene, dinitroftalimide and dinitronaftalimide with dichlorethylenes, ketones, acetylene and methylene "bridged" groups between the phenyl nuclei are given. Forcitation:Kumykov R.M., Vologirov A.K. New aromatic dinitroderivatives of chloral as monomer for synthesys of polyester and polyhetero- arylene. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 2. P. 4-14

Effect of Travel Time and Temperature on Chlorine Bulk Decay in Water Supply Pipes

An experimental study was performed by using the world standard treated drinking water of the city of Ankara. Chlorine is known to be consumed in the bulk liquid phase and at the pipe wall. In the present study the bulk decay pattern was investigated in the absence of pipe wall decay. The test results presented describe how chlorine bulk decay might change with the travel time (residence time) of water in a pipe and the temperature of water in the network. Other than the single constant bulk decay coefficient of chlorine for the first-order exponential decay equation frequently used in many previous studies and models, a parameter coupling residence time of water might be more representative for the water of a city supply network. The test data also showed that chlorine decay of stagnant water in bottles does not differ in magnitude from that of flowing water in a pipe. Additionally, the test results reveal no correlation between initial chlorine concentration level and the bulk decay pattern.

New model of chlorine-wall reaction for simulating chlorine concentration in drinking water distribution systems

Accurate modelling of chlorine concentrations throughout a drinking water system needs sound mathematical descriptions of decay mechanisms in bulk water and at pipe walls. Wall-reaction rates along pipelines in three different systems were calculated from differences between field chlorine profiles and accurately modelled bulk decay. Lined pipes with sufficiently large diameters (>500 mm) and higher chlorine concentrations (>0.5 mg/L) had negligible wall-decay rates, compared with bulk-decay rates. Further downstream, wall-reaction rate consistently increased (peaking around 0.15 mg/dm2/h) as chlorine concentration decreased, until mass-transport to the wall was controlling wall reaction. These results contradict wall-reaction models, including those incorporated in the EPANET software, which assume wall decay is of either zero-order (constant decay rate) or first-order (wall-decay rate reduces with chlorine concentration). Instead, results are consistent with facilitation of the wall reaction by biofilm activity, rather than surficial chemical reactions. A new model of wall reaction combines the effect of biofilm activity moderated by chlorine concentration and mass-transport limitation. This wall reaction model, with an accurate bulk chlorine decay model, is essential for sufficiently accurate prediction of chlorine residuals towards the end of distribution systems and therefore control of microbial contamination. Implementing this model in EPANET-MSX (or similar) software enables the accurate chlorine modelling required for improving disinfection strategies in drinking water networks. New insight into the effect of chlorine on biofilm can also assist in controlling biofilm to maintain chlorine residuals.

Effect of Flow Velocity on Chlorine Decay in Water Distribution Network:A Pilot Loop Study

Experiments were run in the pipe loop setup to estimate bulk and wall chlorine decay rates under varying flow and chlorine levels for groundwater. A recirculating loop of 50 mm inner diameter polyvinyl chloride pipe and a variable flow pump with feed and recirculation tank were used to design a pipe loop. Sodium hypochlorite was introduced as free chlorine into the test water. The study came up with three important findings: (a) bulk chlorine decay rate in test water decreased with increase in chlorine levels, which is attributed to the type and level of organic matter present in test water. (b) Chlorine decay rate in pilot loop setup increased with increase in flow velocity. The result showed that under turbulent conditions, in addition to chlorine, mass flux transfer from bulk to wall and biofilm removal from pipe surface contributed to chlorine decay. We also noted that with increase in flow velocity the contribution of bulk reaction to total chlorine decay in pipe loop decreased. (c) ANOVA test on experimental dataset showed that as compared to initial chlorine levels, flow velocity has statistically significant effect on chlorine dissipation in a pipe loop. We also found that after turbulent flow is achieved, the effect of flow velocity on the wall decay is negligible.

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.

Application and Comparison of Two Chlorine Decay Models for Predicting Bulk Chlorine Residuals

In this study, the factors that leading to loss of chlorine residual in water distribution systems were investigated. A series of experiments performed on real water samples collected from effluent of water treatment plant before chlorination. The results showed that bulk chlorine decay rate varied significantly with the initial chlorine concentration and the organic content of water. Further, this paper explores the performance and the potential applicability of the parallel first order model and second order model to represent the bulk chlorine reactions. The modelling and simulation study lead to define the bulk chlorine coefficients as a function of initial chlorine concentration (Co) and COD by developing mathematical equations related to these parameters.