A field study evaluation for mitigating biofouling with chlorine dioxide or chlorine integrated with UV disinfection

The drinking water industry is continually seeking innovative disinfection strategies to control biofouling in transmission systems. This research, conducted in collaboration with the East Bay Municipal Utility District (EBMUD) in California, compared the efficacy of chlorine dioxide (ClO2) to free chlorine (Cl2) with and without pre-treatment with low-pressure ultraviolet (UV) light for biofilm control. An additional goal was to determine disinfection by-product (DBP) formation with each disinfection strategy. Annular reactors (ARs) containing polycarbonate coupons were used to simulate EBMUD's 90-mile aqueduct that transports surface water from a source reservoir to treatment facilities. ARs were dosed with chemical disinfectants to achieve a residual of 0.2 mg/L, which is a typical value mid-way in the aqueduct. The experiment matrix included four strategies of disinfection including UV/ClO2, ClO2, UV/Cl2 and Cl2. Two ARs acted as controls and received raw water (RW) or UV-treated water. The data presented show that the UV/ClO2 combination was most effective against suspended and attached heterotrophic (heterotrophic plate count, HPC) bacteria with 3.93 log and 2.05 log reductions, respectively. ClO2 was more effective than Cl2 at removing suspended HPC bacteria and similarly effective in biofilm bacterial removal. UV light alone was not effective in controlling suspended or biofilm bacteria compared to treatment with ClO2 or Cl2. Pre-treatment with UV was more effective overall for removal of HPC bacteria than treating with corresponding chemical disinfectants only; however, it did not lower required chemical dosages. Therefore, no significant differences were observed in DBP concentrations between ARs pre-treated with UV light and ARs not pre-treated. Disinfection with ClO2 produced fewer total trihalomethanes (TTHMs) and haloacetic acids (HAAs) than chlorination but did produce low levels of chlorite. These data indicate that replacing Cl2 with ClO2 would further control microbiological re-growth and minimize TTHM and HAA formation, but may introduce other DBPs.     

Sequential UV- and chlorine-based disinfection to mitigate Escherichia coli in drinking water biofilms

This study was designed to examine the potential downstream benefits of sequential disinfection to control the persistence of Escherichia coli under conditions relevant to drinking water distribution systems. Eight annular reactors (four polycarbonate and four cast iron) were setup in parallel to address various factors that could influence biofilm growth in distribution systems. Eight reactors were treated with chlorine, chlorine dioxide and monochloramine alone or in combination with UV to examine the effects on Escherichia coli growth and persistence in both the effluent and biofilm. In general, UV-treated systems in combination with chlorine or chlorine dioxide and monochloramine achieved greater log reductions in both effluent and biofilm than systems treated with chlorine-based disinfectants alone. However, during UV-low chlorine disinfection, E. coli was found to persist at low levels, suggesting that the UV treatment had instigated an adaptive mutation. During UV-chlorine-dioxide treatment, the E. coli that was initially below the detection limit reappeared during a low level of disinfection (0.2 mg/L) in the cast iron systems. Chloramine was shown to be effective in disinfecting suspended E. coli in the effluent but was unable to reduce biofilm counts to below the detection limit. Issues such as repair mechanism of E. coli and nitrification could help explain some of these aberrations. Improved understanding of the ability of chlorine-based disinfectant in combination with UV to provide sufficient disinfection will ultimately effect in improved management and safety of drinking water.     

ClO2消毒涉及毒性问题的探讨

对二氧化氯 Cl O2 消毒无机副产物亚氯酸盐 Cl O2 - 和氯酸盐 Cl O3- 来源进行了分析 ,高浓度的 Cl O2 、Cl O2 - 和 Cl O3- 的毒性主要与血液系统有关 ,在相当于人饮用 Cl O2 、Cl O2 - 和 Cl O3- 混合溶液 1 60倍的动物血液常规检测中未发现异常 ,Ames试验显示试验浓度的 Cl O2 、Cl O2 - 和 Cl O3-水溶液不具有致突变作用 .     

Effects of disinfectant and biofilm on the corrosion of cast iron pipes in a reclaimed water distribution system

The effects of disinfection and biofilm on the corrosion of cast iron pipe in a model reclaimed water distribution system were studied using annular reactors (ARs). The corrosion scales formed under different conditions were characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and scanning electron microscopy (SEM), while the bacterial characteristics of biofilm on the surface were determined using several molecular methods. The corrosion scales from the ARs with chlorine included predominantly α-FeOOH and Fe₂O₃, while CaPO₃(OH)·2H₂O and α-FeOOH were the predominant phases after chloramines replaced chlorine. Studies of the consumption of chlorine and iron release indicated that the formation of dense oxide layers and biofilm inhibited iron corrosion, causing stable lower chlorine decay. It was verified that iron-oxidizing bacteria (IOB) such as Sediminibacterium sp., and iron-reducing bacteria (IRB) such as Shewanella sp., synergistically interacted with the corrosion product to prevent further corrosion. For the ARs without disinfection, α-FeOOH was the predominant phase at the primary stage, while CaCO₃ and α-FeOOH were predominant with increasing time. The mixed corrosion-inducing bacteria, including the IRB Shewanella sp., the IOB Sediminibacterium sp., and the sulfur-oxidizing bacteria (SOB) Limnobacter thioxidans strain, promoted iron corrosion by synergistic interactions in the primary period, while anaerobic IRB became the predominant corrosion bacteria, preventing further corrosion via the formation of protective layers.     

从DOC、AOC的变化分析二氧化氯消毒工艺

考察了二氧化氯（CIO2）及其组合消毒工艺中溶解性有机物（DOC）浓度和可同化有机碳（AOC）浓度的变化规律。结果表明,以DOC表征的有机物浓度在消毒反应前后变化不大;CIO2的强氧化能力体现在将高分子有机物氧化成中、小分子有机物方面,氧化产物以草酸类物质为主,这导致了AOC浓度的升高,降低了出水的生物稳定性;增加CIO2的投量（〉4mg／L）或与氯胺组合消毒能有效降低出水的AOC浓度,消毒反应24h后出水的AOC浓度均比进水的（59μg/L）低。     

配水管网中二氧化氯和氯联合消毒余氯衰减规律的研究

研究配水管网中二氧化氯和氯联合消毒余氯的衰减规律,分析铸铁管、钢管和PVC管中不同消毒剂投加量下二氧化氯和氯联合消毒的衰减规律。研究结果表明,不同管材中二氧化氯和氯联合消毒衰减速率不同,联合消毒衰减速率低于单独采用二氧化氯的衰减速率。     

Enhanced disinfection efficiency of mechanically mixed oxidants with free chlorine

To the best of our knowledge, this study is the first investigation to be performed into the potential benefits of mechanically mixed disinfectants in controlling bacterial inactivation. The purpose of this study was to evaluate the disinfection efficiency of mechanically mixed oxidants with identical oxidant concentrations, which were made by adding small amounts of subsidiary oxidants, namely ozone (O3), chlorine dioxide (ClO2), hydrogen peroxide (H2O2) and chlorite (ClO2(-)), to free available chlorine (Cl2), using Bacillus subtilis spores as the indicator microorganisms. The mechanically mixed oxidants containing Cl2/O3, Cl2/ClO2 and Cl2/ClO2(-) showed enhanced efficiencies (of up to 52%) in comparison with Cl2 alone, whereas no significant difference was observed between the mixed oxidant, Cl2/H2O2, and Cl2 alone. This enhanced disinfection efficiency can be explained by the synergistic effect of the mixed oxidant itself and the effect of intermediates such as ClO2(-)/ClO2, which are generated from the reaction between an excess of Cl2 and a small amount of O3/ClO2(-). Overall, this study suggests that mechanically mixed oxidants incorporating excess chlorine can constitute a new and moderately efficient method of disinfection.     

Inactivation of enteric microorganisms with chemical disinfectants, UV irradiation and combined chemical/UV treatments

The relative disinfection efficiencies of peracetic acid (PAA), hydrogen peroxide (H2O2) and sodium hypochlorite (NaOCl) against Escherichia coli, Enterococcus faecalis, Salmonella enteritidis and coliphage MS2 virus were studied in laboratory-scale experiments. This study also evaluated the efficiency of combined PAA/ultraviolet irradiation (UV) and H2O2/UV treatments to determine if the microbial inactivation was synergistic. Microbial cultures were added into a synthetic wastewater-like test medium and treated by chemical disinfectants with a 10 min contact time, UV irradiation or the combination of chemical and UV treatments. A peracetic acid dose of 3 mg/l resulted in approximately 2-3 log enteric bacterial reductions, whereas 7-15 mg/l PAA was needed to achieve 1-1.5 log coliphage MS2 reductions. Doses of 3-150 mg/l hydrogen peroxide achieved below 0.2 log microbial reductions. Sodium hypochlorite treatments caused 0.3-1 log microbial reductions at an 18 mg/l chlorine dose, while 2.6 log reductions of E. faecalis were achieved at a 12 mg/l chlorine dose. The results indicate that PAA could represent a good alternative to chlorine compounds in disinfection procedures, especially in wastewaters containing easily oxidizable organic matter. Hydrogen peroxide is not an efficient disinfectant against enteric microorganisms in wastewaters. The combined PAA/UV disinfection showed increased disinfection efficiency and synergistic benefits with all the enteric bacteria tested but lower synergies for the coliphage MS2. This suggests that this method could improve the efficiency and reliability of disinfection in wastewater treatment plants. The combined H2O2/UV disinfection only slightly influenced the microbial reductions compared to UV treatments and showed some antagonism and no synergies.     

Biodegradability of organic by-products after natural organic matter oxidation with ClO2--case study

Apart from well-known chlorites and chlorates, chlorine dioxide also generates easily biodegradable carbonyl compounds and short chain carboxylic acids during water disinfection. The main goal of the presented study was to examine the influence of natural organic matter (NOM) oxidation with chlorine dioxide, on the quantity as well as the quality of formed biodegradable by-products. In the experiments conducted at the pilot plant the sand filtered water (MWI) and ozonated/biofiltrated water (BAF) were oxidised with ClO2. The amount of BDOC formed as a result of the oxidation of both waters with ClO2 was compared. The results showed considerable differences in formation of ClO2 oxidation by-products between non-ozonated and ozonated/biofiltered waters. The disinfection of ozonated/biofiltrated water with ClO2 generated comparable amounts of aldehydes and much higher amounts of carboxylic acids than ClO2 oxidation of sand filtered water. These findings are essential for waterworks with ozonation/biofiltration units and ClO2 disinfection implemented.     

Technical note the pattern of ClO2 stabilized by Na2CO3/H2O2

In this paper, the existing patterns of carbonate and ClO2 in the so-called "stabilized chlorine dioxide" solution which is stabilized by stabilizers Na2CO3 and H2O2 are analyzed. Meanwhile, thermostability, UV absorption spectrum, specificity of the paper chromatogram, microstructure and ionic chromatogram of this solution were studied, and contrasted with pure NaClO2 and ClO2. The results show that ClO2 in "stabilized chlorine dioxide" solution exists in the form of chlorite ClO2-, carbonate exists in the form of bicarbonate. Therefore, it is considered that "stabilized chlorine dioxide" solution is mixed solution of ClO2- and HCO3-, its pH being 8.5.     

Removal of chlorine dioxide disinfection by-products by ferrous salts

Chlorine dioxide when used as an effective disinfectant forms undesirable disinfection by-products, i.e. chlorite and chlorate ions. The aim of this research was to study the removal of these ions by ferrous ions in the presence or absence of oxygen. The efficiency of Fe+2 for ClO2- and ClO3- removal was followed by a determination of their initial and final concentrations, pH and delta Fe+2 consumed/delta ClO2- removed ratios. The optimal weight ratio of delta Fe+2 consumed/delta ClO2- removed for complete ClO2 removal was found to be close to the theoretical calculated value of 3.31. It was proved that ferrous salts can reduce chlorite ions to harmless Cl- ions. This method can be recommended as a part of ClO2 disinfection to ensure safe drinking water, with no harm to water consumers and to the environment.     

Disinfection of swine wastewater using chlorine, ultraviolet light and ozone

Veterinary antibiotics are widely used at concentrated animal feeding operations (CAFOs) to prevent disease and promote growth of livestock. However, the majority of antibiotics are excreted from animals in urine, feces, and manure. Consequently, the lagoons used to store these wastes can act as reservoirs of antibiotics and antibiotic-resistant bacteria. There is currently no regulation or control of these systems to prevent the spread of these bacteria and their genes for antibiotic resistance into other environments. This study was conducted to determine the disinfection potential of chlorine, ultraviolet light and ozone against swine lagoon bacteria. Results indicate that a chlorine dose of 30 mg/L could achieve a 2.2-3.4 log bacteria reduction in lagoon samples. However, increasing the dose of chlorine did not significantly enhance the disinfection activity due to the presence of chlorine-resistant bacteria. The chlorine resistant bacteria were identified to be closely related to Bacillus subtilis and Bacillus licheniformis. A significant percentage of lagoon bacteria were not susceptible to the four selected antibiotics: chlortetracycline, lincomycin, sulfamethazine and tetracycline (TET). However, the presence of both chlorine and TET could inactivate all bacteria in one lagoon sample. The disinfection potential of UV irradiation and ozone was also examined. Ultraviolet light was an effective bacterial disinfectant, but was unlikely to be economically viable due to its high energy requirements. At an ozone dose of 100 mg/L, the bacteria inactivation efficiency could reach 3.3-3.9 log.     

二氧化氯对水中典型菌种的试验研究

研究了二氧化氯（ＣｌＯ２）对水中某些典型细菌的灭菌效果，考察了在消毒剂投量、ｐＨ值及接触时间等不同试验条件下，二氧化氯的灭菌效果．与液氯比较，二氧化氯的灭菌效果优于或与液氯相当．二氧化氯可在广泛的ｐＨ范围内有效地杀灭细菌．     

二氧化氯、氯胺顺序投加联合消毒工艺的研究

以天津市某自来水厂的滤后水为研究对象,采用二氧化氯、氯胺顺序投加联合消毒工艺对其进行消毒处理。运用化学分析和生物学试验的方法,考察了经不同投量的组合消毒后消毒剂残余量的变化,以及联合工艺的消毒效果和持续消毒能力。试验结果表明,经不同投量组合的二氧化氯、氯胺顺序投加联合消毒后,出水中的细菌总数及总大肠菌群均达到《生活饮用水卫生标准》的要求。氯胺投量对总余氯和二氧化氯残余量的影响显著,而二氧化氯的投加量对其残余量的影响不大。二氧化氯、氯胺顺序投加联合消毒工艺在低投量组合下就能达到良好的消毒效果,且持续消毒能力强。     

Adsorption of natural organic matter oxidized with ClO2 on granular activated carbon

The paper describes the influence of the oxidation of natural organic matter (NOM) molecules with chlorine dioxide (ClO2) on granulated activated carbon (GAC) adsorption. In order to determinate the influence of ClO2 dosage on the NOM adsorption on GAC two parallel pilot scale experiments were performed. The raw water was treated respectively with 0.2 and 0.4 mg ClO2 L(-1) followed by the adsorption on GAC filters. Experiments were total organic carbon (TOC) measurements and size exclusion chromatography (SEC) controlled. The molecular weight distribution of NOM in the filtration bed outlet demonstrates that the low molecular weight molecules are less retained than the higher molecular weight components of NOM. It is shown that low molecular weight NOM causes less ClO2 demand. The oxidation of NOM molecules and very high capacity of GAC filter bed for NOM components can be used to control high ClO2 demand.     

Association between haloacetic acid degradation and heterotrophic bacteria in water distribution systems

The occurrences of trihalomethanes (THMs), haloacetic acids (HAAs) and heterotrophic bacteria were monitored in five small water systems over a nine-month period to investigate the association between HAA degradation and heterotrophic bacteria populations. The sampling sites were chosen to cover the entire distribution network for each system. An inverse association between heterotrophic bacteria and HAA concentrations was found at some locations where chlorine residuals were around or less than 0.3 mg L⁻¹. At other sample locations, where chlorine residuals were higher (over 0.7 mg L⁻¹), no HAA reduction was observed. A high heterotrophic bacteria count accompanied with a low chlorine residual could be used as an indicator for HAA degradation in distribution systems.     

Derivation of acute ecological risk criteria for chlorite in freshwater ecosystems

Chlorine dioxide has been proposed as an alternative to chlorine because it is a powerful disinfection agent that does not react with ammonia or chlorinated organics to form chloramines or trihalomethanes. The major reduction product formed when chlorine dioxide is added to water is the chlorite ion. Chlorite has been shown to be less toxic than free or combined chlorine. However, previous studies with eight freshwater families produced a US Environmental Protection Agency (USEPA) acute water quality criteria (WQC) lower than the WQC for chlorine. In the current study, an additional 12 families were added to the toxicological database to determine ecological risk criteria (ERC) using both the standard USEPA WQC methodology and the USEPA Office of Pesticide Programs (OPP) probabilistic approach. Chlorite LC50 values for the 20 family database ranged from 0.27 mg/L for the Daphnidae to 208.76 mg/L for the Salmonidae. The Daphnidae were by far the most sensitive family tested, with an LC50 44 times lower than the next most sensitive family tested, the Hyalellidae (LC50=1.19 mg/L) and 214 times lower than the most sensitive fish family tested, the Ictaluridae (LC50=5.79 mg/L). The Criteria Maximum Concentration calculated using the USEPA WQC methodology was 0.025 mg/L while the 95% ERC calculated using the USEPA OPP probabilistic methodology was 0.135 mg/L. The USEPA OPP probabilistic approach yields a criterion more consistent with the overall species sensitivity distribution and is not overly skewed by the low Daphnidae LC50 as is the USEPA WQC approach.     

二氧化氯对水中细菌的灭菌效果

通过对不同消毒剂投量、接触时间和ＰＨ值等条件研究，证明ＣｌＯ２来菌效果优于或相当于液氯。ＣｌＯ２可在广泛的ＰＨ值范围内具有较强的灭菌能力，而液氯仅在ＰＨ６．８－８．５范围内具有较强的灭菌能力。还初步探讨了ＣｌＯ２对细菌的杀灭机理。研究结果表明，ＣｌＯ２是一种优良的替代消毒剂。     

Formation of aldehydes upon ClO2 disinfection

Carbonyl compounds are considered to be the most common ozonation by-products. Apart from well-known chlorites and chlorates, chlorine dioxide (ClO(2)) also generates organic by-products. The goal of this paper is an investigation into the influence of disinfection with ClO(2) on the aldehydes formation. Three types of waters were disinfected with different doses of ClO(2) at the various pH values. The results of size exclusion chromatography show that the reaction of ClO(2) with humic fraction of natural organic matter proceeds mainly on an aromatic part of the molecules. The results obtained indicate that the level of carbonyls concentration can significantly increase with the time of ClO(2) reaction with carbonyl precursors in treated water. There is no noticeable correlation between quantity of aldehydes and pH value of disinfected water. The range of "productivity" of aldehydes in water treated with chlorine dioxide is similar to the range estimated for the carbonyls formed upon ozonation.     

Nucleic acid fluorochromes and flow cytometry prove useful in assessing the effect of chlorination on drinking water bacteria

Flow cytometry (FCM), combined with staining using two fluorochromes (propidium iodide, PI, or SYBR Green II RNA gel stain, SYBR-II), was used to assess nucleic acid injuries to chlorinated drinking water bacteria. Highly fluorescent SYBR-II-stained bacteria were converted to bacteria with low fluorescence after chlorination. PI staining of bacteria exposed to different doses of chlorine showed membrane permeabilisation ([Cl2] < 0.2 mg L(-1)) and nucleic acid damage at higher doses ([Cl2] > 0.3 mg L(-1)). Above a threshold dose (between 1.5 and 3 mg Cl2 L(-1)), nucleic acids appeared severely damaged and incapable of being stained by PI or SYBR-II. These results constitute evidence that FCM is a promising tool for assessing drinking water bacteria injuries and for controlling chlorine disinfection efficiency much more rapidly than the standard sensitive but time-consuming heterotrophic plate count method.