Effects of Bromide Ion and Natural Organic Matter Fractions on the Formation and Speciation of Chlorination By-Products

The impacts of bromide concentration and natural organic matter (NOM) characteristics on the formation and speciation of disinfection by-products (DBPs) in chlorinated NOM fractions were investigated. A total of 20 bulk water NOM fractions with a wide range of specific ultraviolet (UV) absorbance (SUVA254) values were obtained from a source water employing XAD-8 or XAD-4 resin adsorption in completely mixed batch reactors. SUVA was not a good predictor of DBP [trihalomethanes (THMs), haloacetic acids (HAAs), and adsorbable organic halogens (AOX)] formation and speciation. The destruction in the UV254 absorbance from chlorination did not correlate with DBP formation at any bromide level. NOM moieties which do not absorb UV light at 254?nm significantly contributed to DBP formation. Mass balance calculations on halogens using THMs, HAAs, and AOX data indicated that significant amounts of DBPs (>54% of AOX) other than THMs and HAAs were formed in NOM fractions with 60–110?μg/L bromide concentration. The relative occurrence of such other halogenated by-products decreased with increasing bromide concentrations up to 500?μg/L level. NOM in the studied water was more susceptible to the formation of brominated THM species as opposed to brominated HAAs. At constant dissolved organic carbon concentration, chlorine dose and pH, increasing bromide concentrations in NOM fractions increased the total concentrations of DBPs and resulted in a shift toward the formation of brominated species. Further, increasing bromide concentrations increased the spectrum of detected species (i.e., occurrence of all nine HAAs) and provided a competitive advantage to THM and HAA precursors in NOM over precursors of other DBPs.     

Development of Optimal Poly-Alumino–Iron Sulphate Coagulant

An optimal prepolymerized inorganic coagulant, poly-alumino–iron sulphate (PAFS), was developed and examined for drinking water treatment. PAFS is a new type of prehydrolyzed metal–ion coagulant. An investigation of the conditions for preparing PAFS has been conducted using Al2(SO4)3 with Fe2(SO4)3 as primary raw materials. Optimization of the preparation conditions of the PAFS involved variation of the total metal–ion concentration, oxidation temperature, the molar ratio of the oxidant to metal–ion, and the oxidation period. An evaluation of the coagulation performance with two types of test waters showed that selected PAFS coagulants achieved either a greater or similar removal in terms of percentages of color, UV(254?nm) absorbance and dissolved organic carbon in comparison with another polymeric coagulant, polyferric sulphate (PFS). However, both of these (PAFS and PFS) had a superior performance to ferric sulphate (FS) and aluminum sulphate (AS). Of particular significance was that PAFS achieved the lowest residual metal–ion concentrations, Fe and Al, in comparison with PFS, FS, and AS, respectively.     

稀土对聚硅酸硫酸盐絮凝剂稳定性及絮凝效果的影响

研究了稀土一聚硅酸硫酸铁(RE-PFSS)和稀土一聚硅酸硫酸铝(RE-PASS)的制备与絮凝性能.研究结果表明,稀土与二氧化硅的摩尔比n( RE3+)∶n( SiO2)、陈化时间等因素对其稳定性及絮凝性均产生影响,控制适宜的摩尔比和陈化时间可明显地提高絮凝剂的稳定性和絮凝性能.通过对模拟水样进行絮凝试验表明,稀土一聚硅酸硫酸铁(铝)的稳定性、絮凝效果优于聚硅酸硫酸铝(PASS)、聚硅酸硫酸铁(PFSS).当陈化15天时,RE-PASS和RE-PFSS投加量为0.085mL/L时,絮凝效果最佳.     

Assessment of Trace Estrogenic Contaminants Removal by Coagulant Addition, Powdered Activated Carbon Adsorption and Powdered Activated Carbon/Microfiltration Processes

Increasing attention is being paid to health and environmental risk as a result of the presence of trace steroid estrogens in the effluent discharged from municipal sewage treatment plants. This paper focuses on assessment of removal of these trace compounds using 3H-labeled estrone as the model compound. Jar tests over a range of ferric chloride dosages and pH conditions showed that coagulation was ineffective in removal of estrone from secondary effluent. The experiments showed that the combination of powdered activated carbon (PAC) and microfiltration could be effective for removal of trace estrone from water. The rate and extent of estrone removal by PAC are functions of PAC dosage and retention time of PAC in the system. Mathematical analysis of the results using a homogeneous surface diffusion model indicates that the adsorption of estrone on PAC can be limited by film diffusion and internal surface diffusion. The surface and film mass transfer coefficients were determined to be 1.59×10?9?cm2/min and 0.6 cm/min, respectively, under the conditions used.     

Enhanced Ripening of Slow Sand Filters

While successful in removing turbidity and pathogens from drinking water, slow sand filters require ripening periods at the beginning of each filter run. The premise of this research was that it should be possible to enhance the ripening of slow sand filters. Potential ripening agents were screened by assessing their interaction with the surface of filtration media and turbidity particles. Four natural organic polymers and nine synthetic polymers were investigated for their potential to enhance filter ripening. Of the 13 modifying agents considered, none conclusively sorbed to the filter media, and only one, a synthetic polymer, interacted with kaolin particles. A filter modified with continuous feed of the polymer ripened successfully and produced water with turbidity below 1.0 NTU in about 24 h. Most turbidity removal in the treated filter occurred in the schmutzdecke rather than within the depth of the filter bed. Hence, the mechanism of enhanced ripening in this case probably was particle agglomeration with resulting acceleration of particle deposition at the filter surface accompanied by straining or attachment to previously removed particles.     

Modeling TOC Breakthrough in Granular Activated Carbon Adsorbers

Linear regression techniques were used to develop practical models to predict total organic carbon (TOC) breakthrough in bituminous granular activated carbon (GAC) adsorbers. Models were developed for two field-scale GAC sizes (8×30 and 12×40?mesh) and two empty bed contact times (EBCTs) (10 and 20 min). Model input parameters include two water quality variables, influent TOC concentration (TOC0) and pH, that impact performance. The dependent variables for the models were normalized breakthrough time, throughput in bed volumes, to six fractional (TOC/TOC0 = 0.2, 0.3, 0.4, 0.5, 0.6, and 0.7) and three mass (TOC = 1.0, 1.5, and 2.0 mg/L) effluent concentrations. Model development was performed using small-scale breakthrough data from 35 different source waters; external model validation was performed with small-scale breakthrough data from 14 source waters; a sensitivity analysis was performed to ensure that the models effectively capture expected breakthrough trend; and a scalability test was performed to verify the models’ ability to predict breakthrough for field-scale GAC adsorbers.     

Impact of Particle Aggregated Microbes on UV Disinfection. II: Proper Absorbance Measurement for UV Fluence

Ultraviolet (UV) absorbance measurements are subject to significant error using a standard spectrophotometer when particles or aggregates that scatter light are present. True UV absorbance for highly turbid waters should be measured using integrating sphere (IS) spectrophotometry that allows the collection of reflected and transmitted radiation simultaneously. This is especially important when the effects of scattering impact UV disinfection—such as with the presence of aggregates. The impact of light scattering of particle-aggregated microbes on UV disinfection was evaluated by comparing standard spectrophotometer and integrating sphere absorbance measurements for UV fluence determination. Spore–clay aggregates in simulated drinking waters and spore aggregates with natural particles from raw waters were induced by flocculation with alum. Coagulated systems significantly decreased the UV inactivation effectiveness compared to the noncoagulated system with the effects more pronounced for raw natural water. Absorbance measurement of suspensions and aggregates using standard spectrophotometry in the calculations of fluence resulted in overdosing whereas the use of IS spectroscopy did not. The results demonstrated that aggregation protected spores from UV disinfection, and that use of proper absorbance measurement techniques, accounting for particle scattering, is essential for correct interpretation of the results.     

Rapid Small-Scale Column Tests for Arsenate Removal in Iron Oxide Packed Bed Columns

Arsenate breakthrough in column studies with a porous granular ferric hydroxide (GFH) was investigated in model waters and groundwaters. In this study, the use of rapid small-scale column tests (RSSCTs) initially designed for simulating the removal of organic compounds by granular activated carbon was extended for arsenate adsorption onto GFH. Adsorption kinetic studies and a comparison of laboratory RSSCT performance versus pilot-scale performance suggests that proportional diffusivity (PD) RSSCT scaling approaches are more valid than constant diffusivity (CD) approaches for arsenate onto GFH. Adsorption densities from column tests (qcolumn) were calculated at the point in the breakthrough curve when arsenate equaled 10 μg/L in the column effluent. For a simulated 2.5 min empty-bed contact time (EBCT), a model water (pH=8.6) had qcolumn values of 0.99 to 1.5 mgAs/gGFH versus 0.02 to 0.28 mgAs/gGFH with a comparable pH and EBCT in a natural groundwater. The differences were attributed to the silica, phosphate, vanadium, and other adsorbable inorganics in the groundwater. At pH 7.6 to 7.8, qcolumn values from PD-RSSCTs in the three natural waters were comparable (1.5±0.3 mgAs/gGFH) and higher than CD-RSSCT qcolumn values (0.57±0.26 mgAs/gGFH) in the three natural waters. All the RSSCTs captured changes in water quality (source water and pH) and operational regimes (e.g., EBCTs) and could be used to aid in the selection and design of arsenic removal media for full-scale treatment facilities.     

Modeling the Transformation of Chromophoric Natural Organic Matter during UV/H2O2 Advanced Oxidation

This research developed a differential kinetic model to predict the partial degradation of natural organic matter (NOM) during ultraviolet plus hydrogen peroxide (UV/H2O2) advanced oxidation treatment. The absorbance of 254?nm UV, representing chromophoric NOM (CNOM) was used as a surrogate to track the degradation of NOM. To obtain reaction rate constants not available in the literature, i.e., reactions between the hydroxyl radical (?OH) and NOM, experiments were conducted with “synthetic” water, using isolated Suwannee River NOM, and parameter estimation was applied to obtain the unknown model parameters. The reaction rate constant for the reaction between ?OH and total organic carbon (TOC), k?OH,TOC, was estimated at 1.14(±0.10)×104??L?mg-1?s-1, and the reaction rate constant between ?OH and CNOM, k?OH,CNOM, was estimated at 3.04(±0.33)×104??L?mol-1?s-1. The model was evaluated on two natural waters to predict the degradation of CNOM and H2O2 during UV/H2O2 treatment. Model predictions of CNOM degradation agreed well with the experimental results for UV/H2O2 treatment of the natural waters, with errors up to 6%. For the natural water with additional alkalinity, the model also predicted well the slower degradation of CNOM during UV/H2O2 treatment, owing to scavenging of ?OH by carbonate species. The model, however, underpredicted the degradation of H2O2, suggesting that, when NOM is present, mechanisms besides the photolysis of H2O2 contribute appreciably to H2O2 degradation.     

Particle Destabilization in Highway Runoff to Optimize Pollutant Removal

Sedimentation column studies and simulations using particle size distribution suggest that low removal efficiencies of smaller particles in highway runoff would be obtained using sedimentation if coagulation-flocculation is not performed. Coagulation-flocculation studies, using metal salts (alum and ferric chloride) and one organic polymer in three molecular weights, were evaluated over the 2004–2005 storm seasons. Only the first flush or approximately the first hour of runoff was coagulated. Efficiencies were quantified with particle size distribution measurements and turbidity. Results with low dosages of metal salts were ineffective and did not improve water quality. High dosages of metal salts using a sweep floc mechanism were effective in dramatically lowering runoff turbidity, but resulted in large quantities of sludge production and required pH control. A cationic organic polymer at low dosages (<10?mg/L) was effective in coagulating highway runoff and reducing particle charge. Extended mixing time was required to achieve low turbidities ( ～ 5 NTU). A combination of organic polymer, followed by small doses of alum (<10?mg/L), reduced mixing time and produced high quality effluent.     

Assessment of Low pH Coagulation Performance Using Fluorescence Spectroscopy

Optimization of organic matter (OM) removal is of key importance for effective water treatment, as its presence affects treatment processes. In particular, OM increases the operational cost of treatment caused by increased coagulant and disinfectant demands. In the work reported here, fluorescence spectroscopy is used to assess the effect of changing coagulation pH on OM removal, character, and composition. The results of a 3-month trial of low pH coagulation operation at a major surface water treatment works in the Midlands region of the UK are discussed, together with the effect upon total organic carbon (TOC) removal. OM removal was assessed on the basis of both measured removal and fluorescence-inferred removal (through intensity-reduction measurements). Fluorescence spectroscopy demonstrated that optimized coagulation affects the quantitative and qualitative OM properties. Fluorescence analyses were shown to complement other OM measurements, with reductions of peak intensities correlating well with removal of TOC in a range of different treatment conditions.     

Trihalomethane and Haloacetic Acid Disinfection By-Products in Full-Scale Drinking Water Systems

Trihalomethane (THM), haloacetic acid (HAA5), and total organic carbon (TOC) data provided by the Missouri Dept. of Natural Resources for drinking water treatment systems in the State of Missouri was analyzed for the years 1997–2001. These data indicated that a significant portion of systems exceeded the current regulatory limits of 80 and 60?μg/L for THM and HAA5 in these years. The vast majority of the treatment plants exceeding the regulatory limits were small plants with service populations less than 10,000 people. No significant temporal trend in either THM or HAA5 was noted for the years 1997–2001. This work suggests that the proposed use of a locational running annual average may have a significant effect on compliance. The use of chloramines (combined chlorine) versus free chlorine (HOCl/OCl?) as a residual disinfectant was shown to significantly reduce both THM and HAA5 in systems that treat their own water (primary systems), but did not have a significant effect in systems which purchase their water from primary systems (secondary systems). Comparison of finished water at the treatment plant versus in the distribution system suggested that a majority of THM and HAA5 may be produced within the plant as opposed to the distribution system. Hence, reducing these chlorinated disinfection byproducts within the treatment plant itself should be a key focus for achieving compliance, and supports Environmental Protection Agency disinfection byproducts compliance guidelines using enhanced coagulation.     

Prediction and Measurement of Bubble Formation in Water Treatment

Water utilities can experience problems from bubble formation during conventional treatment, including impaired particle settling, filter air binding, and measurement as false turbidity in filter effluent. Coagulation processes can cause supersaturation and bubble formation by converting bicarbonate alkalinity to carbon dioxide by acidification. A model was developed to predict potential bubble formation during coagulation, and its accuracy was confirmed using an apparatus designed to physically measure the actual volume of bubbles formed. Alum acted similar to hydrochloric acid for initializing bubble formation, and higher initial alkalinity, lower final solution pH, and increased mixing rate tended to increase bubble formation.     

Strategic Filter Backwashing Techniques and Resulting Particle Passage

A new filter backwashing strategy, extended terminal subfluidization wash (ETSW), aimed at reducing particle passage into the filtered water during the initial filter ripening sequence immediately following backwashing has been evaluated on pilot-scale filters at a conventional water treatment plant using alum as the sole coagulant. Turbidities and particle counts were measured following backwashes extending across a range of ETSW flow rates. The ETSW procedure was effective in significantly reducing the passage of particles through filters that originated from the backwash remnant water flowing out of the filter during the first 20?min of the filter run. A secondary turbidity peak associated with the filter influent water leaving the filter was observed following all fluidization backwashes with or without the addition of air-scour or ETSW. The secondary peak was termed the “additional collector” peak and was attributed to cold-water impaired (CWI) alum coagulation at the plant. The secondary peak was not observed with the particle counter as it was with the turbidimeter, which indicates the particles passing were predominantly particles <2?μm in diameter. A backwash procedure consisting of only subfluidization water flow was evaluated because it was expected to leave significantly higher number of particles attached to the media grains to serve as “additional collectors.” The subfluidization wash procedure virtually eliminated all filter ripening peaks in spite of the CWI coagulation conditions.     

Removal of Emulsified PHCs from Brackish Water by Coagulation

Chemical coagulation is a well-known method for removing colloidal particles that cause turbidity in water. In this study coagulation was used to remove emulsified petroleum hydrocarbons (PHCs) found in fuel oils from brackish water. Comparison of the total ion chromatograms of PHCs before and after coagulation clearly showed that PHCs with carbon numbers between 11 and 35 (naphthalene to pentatriacotane) with long chain alkanes were removed completely from the brackish water by coagulation followed by settling. Smaller carbon number (C7–C9) benzene derivatives were partially removed. For the PHCs with smaller carbon numbers, the removal efficiency increased with increasing carbon number.     

Effects of Sodium Chloride on the Performance of a Sequencing Batch Reactor

In this study, we investigated the effects of sodium chloride (concentrations ranging from 0?to?60?g/L) on the performance of sequencing batch reactors (SBRs) using a microbial culture developed from a domestic sewage treatment plant. The lab-scale SBRs were fed with synthetic wastewater (acetate as the organic substrate) containing either sodium chloride solution or seawater to ensure consistency in feed composition. It was found that sodium chloride concentrations of up to 10?g/L stimulated substrate removal. The organic removal efficiency decreased from 96%, when no sodium chloride was added, to 86% when 60?g/L of sodium chloride was introduced into the influent wastewater. Effluent turbidity increased significantly when the sodium chloride concentration in the wastewater was equal to or above 30?g/L even though the sludge volume index (SVI) decreased. The increase in effluent turbidity could be caused by the release of nondissolved cellular components due to plasmolysis of microorganisms as observed by scanning electron microscopy. Experiments involving seawater (with 20?g/L total dissolved solids) showed that organic removal efficiency improved from 87 to 95% while effluent turbidity and SVI values were lowered when the loading rate parameter (Li) was lowered from 0.6?to?0.3?mg total chemical oxygen demand (mg?VSS?day). Optical microscopy and scanning electron microscopy indicated morphological changes in the microbial population. From this study, it was concluded that microbial culture from domestic wastewater facilities could be acclimated in a SBR to treat wastewater containing sodium chloride concentrations of up to 60?g/L.     

Floc Characteristics and Removal of Turbidity and Humic Acid from High-Turbidity Storm Water

This study considered the removal efficiency of turbidity and organic content from high-turbidity storm water of tropical storm Nari, using polyaluminum chloride (PACl) as a coagulant. The resulting floc size and compactness (fractal dimension) were determined using a small-angle light scattering technique. The response surface method, and the Box-Behnken design, was adopted to examine how the hydrogen ion concentration (pH), turbidity, and alkalinity of the suspension, the PACl dosage, and the dosed amount of humic acid affect the removal efficiency. Flocs with a looser interior structure more efficiently removed turbidity and humic acid. An acidic suspension and moderate PACl dosage and alkalinity level favor the production of loose flocs. Optimal conditions for generating large flocs includé pH neutrality and high PACl dosage. Producing both large and loose flocs depends on a compromise. The removal of turbidity/humic acid from high-turbidity storm water does not proceed by a charge neutralization mechanism.     

Fluidized Bed for Removing Iron and Acidity from Acid Mine Drainage

A fluidized bed reactor (FBR) for the removal of iron from acid mine drainage (AMD) was evaluated as part of a prototype multistage system, which included a bioreactor to oxidize ferrous iron, an FBR for the precipitation of ferric iron as a coating on media, and a carbonate bed (CB) for pH control. In the integrated system, a 99% iron removal efficiency was achieved, with effluent iron concentration remaining <3 mg L?1 and pH >6. The optimum pH for iron removal in the FBR was about pH 3.5. Above that pH, and above an iron loading of about 0.20 mg Fe h?1m?2 reactor surface area, suspended iron particles developed in the reactor system. Particulates in the feed had an adverse impact on the removal performance of the system. Schwertmannite appeared to be the predominant mineral formed in the precipitation reactor. Coating growth on the sand media appeared to result from the attachment and consolidation of small iron particles (<1.0 μm) that formed in the bulk solution.     

One-Step Ambient Temperature Ferrite Process for Treatment of Acid Mine Drainage Waters

A novel approach toward the removal of iron and nonferrous metals from typical South African acid mine drainage (AMD) waters was investigated. The approach involves the controlled oxidation of ferrous-containing AMD water at ambient temperatures in the presence of magnetite seed. The resulting oxidation product is the ferrite (M123+M22+O4) magnetite (Fe3O4) which has the capacity for nonferrous metal removal by cation substitution. M?ssbauer spectroscopy, x-ray diffraction, and scanning electron microscopy analyses confirmed the precipitant to be magnetite. The effects of four parameters are reported: airflow rate, seed concentration, pH, and temperature. All of these independently affect the % ferrous in the final precipitant. In all experiments, the airflow rate was found to be rate limiting with respect to the kinetics of ferrous removal. The retention time for the complete removal of 1,200 mg Fe/L was 0.3–1.6 h (corresponding to airflow rates of 0.05–0.6 L/min, respectively). The precipitant settled well and showed complete stability at pH 5. The total iron concentration in the raw effluent was always less than 1 mg/L, representing an iron removal efficiency of greater than 99.9%.     

Ceramic Filters Impregnated with Silver Nanoparticles for Point-of-Use Water Treatment in Rural Guatemala

The technological performance and social acceptance of ceramic water filters impregnated with silver nanoparticles for point-of-use water treatment were investigated in the laboratory and in the field in the Guatemalan highland community of San Mateo Ixtatán. In the laboratory, filters were constructed with clay and sawdust collected from the Guatemalan community and were tested to determine the effects of percent sawdust and silver nanoparticle treatment on the transport and removal of E. coli. For ceramic filters without silver treatment, size-exclusion and/or sorption is the mechanism of removal and a lower mass-percent sawdust corresponds to greater bacteria removal. The addition of silver nanoparticles to the ceramic filters improved the performance for all mass percentages of sawdust relative to filter media without nanoparticle treatment. Filters with higher porosity achieved higher bacteria removal than those with lower porosity, suggesting an increase in burnable material percentage is advantageous, assuming structural integrity is not compromised. Subsequent to laboratory testing, ceramic filters were manufactured with local materials and labor in San Mateo Ixtatán, Guatemala, and distributed to 62 households in this peri-urban community. The study participants were randomly divided into two groups, and filters were tested periodically over 23?months or 12?months. Filtered effluent samples were tested for turbidity reduction, bacteria removal, and silver leaching. Over the course of the study, the average percent reduction in total coliforms and E. coli was 87% and 92%, respectively. The average effluent turbidity was 0.18 nephelometric turbidity units (NTUs) and average effluent concentration of ionic silver was 0.02??mg/L (below the U.S. EPA standard of 0.1??mg/L). Filters distributed to the second study group consistently performed better than the first study group as manufacturing techniques improved and contact with researchers increased. Overall, users were satisfied with the filters, citing them as easy to use and maintain while improving water quality. The findings of this study suggest that locally manufactured ceramic filters can significantly improve the microbiological quality of water when used as a point-of-use water-treatment technology.