In this paper, the adsorption removal characteristic for 10 species of perfluoroalkyl and polyfluoroalkyl substances (PFAS) was investigated using GAC and modified GAC (GAC-Cu). After modification with Cu(II), the amount of copper was to 1.93 and 4.73 mg/g for GAC and GAC-Cu, respectively. The total amount of 10 species of PFAS per specific area was obtained to 0.548 and 0.612 ng/m2 for GAC and GAC-Cu, respectively. A series of batch test confirmed lower efficiency was observed with a smaller number of carbon chain length and the removal efficiency of PFCA (perfluoroalkyl carboxylic acids) was lower than that of PFSA (perfluoroalkyl sulfonic acids) with the same carbon chain length. Regarding the pH effect, the adsorption capacity was decreased with increase of pH due to the increase of electrostatic repulsion. According to pseudo first and second order (PFO and PSO) kinetic models, while the values of equilibrium uptake and time did not show significant difference, a difference in uptake was observed between 24-48h. Furthermore, based on correlation analysis, Log Kow and uptake have a high correlation with molecular weight (M.W.) and initial concentration, respectively. These results show that long-chain PFAS have higher removal efficiency due to their increased hydrophobicity.
The frequent detection and occurrence of micropollutants (MPs) in aquatic ecosystems has raised public health concerns worldwide. In this study, the behavior of 50 MPs was investigated in three different domestic wastewater treatment plants (WWTPs). Furthermore, the Kruskal-Wallis test was used to assess the geographical and seasonal variation of MPs in the WWTPs. The results showed that the concentrations of 43 MPs ranged from less than 0.1 to 237.6 μg L-1, while other seven MPs including 17-ethynylestradiol, 17-estradiol, sulfathiazole, sulfamethazine, clofibric acid, simvastatin, and lovastatin were not detected in all WWTPs. Among the detected MPs, the pharmaceuticals such as metformin, acetaminophen, naproxen, and caffeine were prominent with maximum concentrations of 133.4, 237.6, 71.5, and 107.7 μg L-1, respectively. Most perfluorinated compounds and nitrosamines were found at trace levels of 1.2 to 55.3 ng L-1, while the concentration of corrosion inhibitors, preservatives (parabens), and endocrine disruptors ranged from less than 0.1 to 4310.8 ng L-1. Regardless of the type of biological treatment process such as MLE, A2O, and MBR, the majority of pharmaceuticals (except lincomycin, diclofenac, iopromide, and carbamazepine), parabens (except Methyl paraben), and endocrine disruptors were removed by more than 80%. However, the removal efficiencies of certain MPs such as atrazine, DEET, perfluorinated compounds (except PFHxA), nitrosamines, and corrosion inhibitors were relatively low or their concentration even increased after treatment. The results of statistical analysis reveal that there is no significant geographical difference in the removal efficacy of MPs, but there are temporal seasonal variations in all WWTPs.
Conventional wastewater treatment plants (WWTPs) do not fully remove micropollutants. Enhanced treatment of sewage effluents is being considered or implemented in some countries to minimize the discharge of problematic micropollutants from WWTPs. Representative enhanced sewage treatment technologies for micropollutant removal were reviewed, including their current status of research and development. Advanced oxidation processes (AOPs) such as ozonation and UV/H2O2 and adsorption processes using powdered (PAC) and granular activated carbon (GAC) were mainly discussed with focusing on process principles for the micropollutant removal, effect of process operation and water matrix factors, and technical and economic feasibility. Pilot- and full-scale studies have shown that ozonation, PAC, and GAC can achieve significant elimination of various micropollutants at economically feasible costs(0.16-0.29 €/m3). Considering the current status of domestic WWTPs, ozonation and PAC were found to be the most feasible options for the enhanced sewage effluent treatment. Although ozonation and PAC are all mature technologies, a range of technical aspects should be considered for their successful application, such as energy consumption, CO2 emission, byproduct or waste generation, and ease of system construction/operation/maintenance. More feasibility studies considering domestic wastewater characteristics and WWTP conditions are required to apply ozonation or PAC/GAC adsorption process to enhance sewage effluent treatment in Korea.
Due to the large-scale production and use of synthetic chemicals in industralized countries, various chemicals are found in the aquatic environment, which are often termed as micropollutants. Effluents of municipal wastewater treatment plants (WWTPs) have been identified as one of the major sources of these micropollutants. In this article, the current status of occurrence and removal of micropollutants in WWTPs and their management policies and options in domestic and foregin countries were critically reviewed. A large number of pharmaceuticals, personal care products, and industrial chemicals are found in WWTPs’ influent, and are only partially removed by current biological wastewater treatment processes. As a result, some micropollutants are present in WWTPs’ effluents, which can negatively affect receiving water quality or drinking water source. To better understand and assess the potential risk of micropollutants, a systematic monitoring framework including advanced analytical tools such as high resolution mass spectrometry and bioanalytical methods is needed. Some Western European countries are taking proactive approach to controlling the micropollutants by upgrading WWTP with enahnced effluent treatment processes. While this enahnced WWTP effluent treatment appears to be a viable option for controlling micropollutant, its implementation requires careful consideration of the technical, economical, political, and cultural issues of all stakeholders.
Applicability of corrosion inhibitor was evaluated using pilot scale water distribution pipe simulator. Calcium hydroxide was used as corrosion inhibitor and the corrosion indices of the water were investigated. Corrosion indices, Langelier saturation index (LI) increased by 0.8 and calcium carbonate precipitation potential (CCPP) increased by 9.8 mg/L. This indicated that corrosivity of water decreased by corrosion inhibitor and the effects lasted for 18 days. Optimum calcium hydroxide dose was found to be 3~5 mg/L for corrosion inhibition. We suggest that monitoring of CCPP as well as LI need to be conducted to control corrosivity of water.
In order to determine the optimal water intake point, the distribution of blue-Green algae and water quality factors in relation to the depth of the Mulgum and Maeri stations located downstream of the Nakdong River were investigated from Jun. 2015 to Sep. 2016. When the current surface water intake system was converted to the deep water intake system, Chl-a concentration and blue-Green algae were reduced by 64.1% and 80.5%, respectively. Microcystin-LR was reduced by 50% to 100%, while geosmin and 2-MIB of the odorant substances were reduced by 42.9% and 11.8%, respectively. The water quality factors such as pH, water temperature, TOC and COD were gradually decreased by 30% in deep water. Therefore, if we used the deep water intake system selectively in the summer season when blue-Green algae masses occur, the concentration of the influx of blue-green algae and its by-products can be expected to decrease, leading to reduced operation costs in tap water production and improved of raw water quality.
The H water treatment plant has been operating since 1982 and has had no renovation. It is assumed that the filters have been operated for more than 30 years and therefore are deteriorated. Many of the filters show an unequal state of air scouring during backwashing. For this study one filter, which was presumed most deteriorated among eighteen filters, was selected as a model filter for renovation. Some of the effects seen after renovation of the underdrain system were a lower average filtrated turbidity by approximately 0.02 NTU and an equal backwash state throughout the filter bed. Sand wash efficiencies by backwash before renovation of the underdrain system were 28%, 8%, and 5% at the surface, 50 cm depth, and 100 cm depth, respectively, and after renovation of the underdrain system were 94%, 26%, and 15% , respectively. The standard deviation of the effective sand size was 0.025-0.033 mm before renovation of the underdrain system and 0.002-0.011 mm after renovation of the underdrain system, meanings there was equal backwash pressure throughout the filter. Filtration time after renovation was approximately 2 times longer than before renovation.
In this study, we have investigated to find optimal pre-treatment flocculation condition by analyzing the floc growth rate with mixing conditions and the membrane permeation flux for pre-treatment step of the membrane process. The higher mixing intensity showed a constant floc size index (FSI) values, and lower mixing intensity increased the degree of dispersion of the FSI values. Results of comparing the distribution characteristics of the FSI value and the permeation flux were more effective in increasing flux when the FSI values were 0.2 or higher. The degree of dispersion of FSI was relatively large in 40 rpm mixing condition compared to 120 rpm. In 40 rpm mixing condition, it decreased the permeation flux compared to 120 rpm because various sizes of flocs were distributed. Coagulation-UF membrane process enhanced 30%∼40% of the flux rate compare to UF alone process, and the coagulation-MF process increased up to 5% of the flux rate compare to MF alone process. Pre-treatment, that is, coagulation process, has been found to be less effects on relatively larger pore size for MF membrane. For UF membrane, the flux was a little bit same when applying only the rapid mixing process or rapid mixing with slow mixing processes together. In case of MF membrane, the flux was improved when rapid mixing process applied with slow mixing process together.
The analytical method for 16 organophosphorus pesticides was developed in this study. The 16 organophosphorus pesticides were analyzed by liquid chromatography-tandem mass spectrometry (LC/MS/MS) using on-line solid phase extraction (on-line SPE) with PLRP- S cartridge. Analysis of all analytes in the MS/MS was processed in the electrospray ioni-zation (ESI) positive mode. They are Azinphos ethyl, Chlorfenvinphos, Ethion, Famphur, Phosmet, Phosphamidon, Terbufos, Aspon, Chlorpyrifos-methyl, Crotoxyphos, Dichlofenthi-on, Dicrotophos, Fonofos, Thionazin, Dimethoate and Iprobenfos. Limits of detection (LODs) and Limits of quantification(LOQs) were obtained as 0.8~2.0 ng/L and 2.6~6.4 ng/L, respectively. All compounds were not detected at the 8 sampling points of the raw water and clean water.
In Korea, many drinking water treatment plants (DWTPs) have introduced and are going to introduce biological activated carbon (BAC) process to treated dissolved organic matter (DOM) in water which are difficult to control by conventional water treatment processes. Even though more decade have passed since introduced BAC in Korea, most of BAC operating method was followed to the modified sand filter operating manuals. In case of BAC backwashing, many DWTPs set the periods of backwashing about 3∼5 days.
In this study, we have collected data to set the proper BAC backwashing periods from both pilot-plant and real DWTPs. We had measured heterotrophic plate count (HPC), turbidity, water temperature, dissolved organic carbon (DOC) and headloss from just after backwashing to the next backwashing time for two years. Considering water quality factors, the BAC run time from backwashing to the next backwashing could extend more 30 days without water quality deterioration if the head loss do not reach the limited level which depends on each BAC facilities’ condition. It means the BAC treated water could be saved in the proportion of extended the backwashing period to the existing backwashing period.
This study carried out continuous column test for estimating the regeneration efficiency with regeneration times and temperatures. More times regenerated granular activated carbon (GAC) has more ash in the GAC and has less apparent density. Two times regenerated GAC (2nd re-GAC) could removed the Trihalomethanes (THMs) in the water for the first two week after starting continuous column test, on the other hand five times regenerated GAC (5th re-GAC) did not have adsorption capacity. The THMs concentration in the effluent was almost equal or higher than that of influent at the first time of continuous column test. 2nd re-GAC showed much more DOC adsorption capacity than 5th re-GAC and the GAC which was regenerated with 700 ℃ had highest DOC removal efficiency among the GACs with 600, 700, 800, 900 ℃ regeneration temperatures. It is anticipated the cost of GAC regeneration could be saved more 100 million won by reducing the furnace temperature of 3rd~4th and 5th~6th about 150 ℃ compared to the current regeneration condition.
This research was performed by means of several different virgin granular activated carbons (GAC) made of each coal, coconut and wood, and the GACs were investigated for an adsorption performance of iodine-131 in a continuous adsorption column. Breakthrough behavior was investigated that the breakthrough points of the virgin two coals-, coconut- and wood-based GACs were observed as bed volume (BV) 7080, BV 5640, BV 5064 and BV 3192, respectively. The experimental results of adsorption capacity (X/M) for iodine-127 showed that two coal- based GACs were highest (208.6 and 139.1 μg/g), the coconut-based GAC was intermediate (86.5 μg/g) and the wood-based GAC was lowest (54.5 μg/g). The X/M of the coal-based GACs was 2∼4 times higher than the X/M of the coconut-based and wood-based GACs.
The tap water is generally known to be corrosive in the pH range at 6.5 ~ 7.5. And the degree of corrosion varies depending on the types of raw water such as river surface water or lake water of the dam. Although several corrosion index represents the corrosivity of tap water, the typical corrosion indexes such as Langelier saturation index (LI) and calcium carbonate precipitation potential (CCPP) were calculated to monitoring the corrosive water quality about raw and tap water in water distribution system. To control the corrosive water quality, the correlation between corrosion index and water quality factors were examined. In this study, corrosion index (LI, CCPP) and the pH was found to be most highly correlated.
Formation of disinfection by-products (DBPs) including trihalomethans (THMs) and haloacetic acids (HAAs) from chlorination of six different species (Chlorella vulgaris, Scenedesmus sp., Anabaena cylindrical, Microcystis aeruginosa, Asterionella formosa and Aulacoseira sp.) of algal extracellular organic matter (EOM). The EOM characteristics evaluation of six algal species reaching at the stationary phase in the growth curve showed most of its SUVA254 showed below 1 and this means hydrophilic organic matter is much higher than hydrophobic organic matter. Chloroform formation potential (CFFP), dichloroacetic acid formation potential (DCAAFP) and trichloroacetic acid formation potential (TCAAFP) were mainly composed of THMFP and HAAFP in the EOM of various algal species. In the case of THMFP/DOC and HAAFP/DOC values, EOM of blue-green algae has appeared highest and EOM of green algae and diatom in order. THMFP/DOC was higher than HAAFP/DOC in EOM of blue-green algae. In comparison of formation potential by unit DOC composed of HAAFP in algal species EOM, DCAAFP/DOC was 1.5 times to 7.5 time higher than TCAAFP/DOC in the EOM of blue-green algae, while DCAAFP/DOC was found to be relatively high compared to TCAAFP/DOC in the EOM of green algae and diatom.
This study accessed the adsorption characteristics of the 9 trihalomethanes (THMs) on coal-based granular activated carbon (GAC). The breakthrough appeared first for CHCl3 and sequentially for CHBr2Cl, CHBr3, CHCl2I, CHBrClI, CHBr2I, CHClI2, CHBrI2, and CHI3. The maximum adsorption capacity (X/M) for the 9 THMs with apparent breakthrough points ranged from 1,175 μg/g (for CHCl3) to 11,087 μg/g (for CHI3). Carbon usage rate (CUR) for CHCl3 was 0.149 g/day, 5.5 times higher than for CHI3 (0.027 g/day).
A comprehensive fractionation technique was applied to a set of water samples obtained along drinking water treatment process with ozonation and biological activated carbon (BAC) process to obtain detailed profiles of dissolved organic matter (DOM) and to evaluate the haloacetic acid (HAA) formation potentials of these DOM fractions. The results indicated that coagulation-sedimentation-sand filtration treatment showed limited ability to remove hydrophilic fraction (28%), while removal of hydrophobic and transphilic fraction were 57% and 40%, respectively. And ozonation and BAC treatment showed limited ability to remove hydrophobic fractions (6%), while removal of hydrophilic and transphilic fractions were 25% and 18%. The haloacetic acid formation potential (HAAFP)/dissolved organic carbon (DOC) of hydrophilic fraction was the highest along the treatment train and HAAFP/DOC of hydrophilic fraction was higher than hydrophobic and transphilic fraction as 23% 30%, because of better removal for hydrophobic fraction both in concentration and reactivity.
Haloacetic acids (HAAs) concentrations have been observed to decreased at drinking water distribution system extremities. This decrease is associated with microbiological degradation by pipe wall biofilm. The objective of this study was to evaluate HAAs degradation in a drinking water system in the presence of a biofilm and to identify the factors that influence this degradation. Degradation of monochloroacetic acid (MCAA), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) was observed in a simulated distribution system. The results obtained showed that different parameters came into play simultaneously in the degradation of HAAs, including retention time, water temperature, biomass, and composition of organic matter. Seasonal variations had a major effect on HAAs degradation and biomass quantity (ATP concentration) was lower by 25% in the winter compared with the summer.
Seven tetracycline classes of antibiotics were treated using ultraviolet (UV) and UV/H2O2 oxidation. Two different UV lamps were used for the UV and UV/H2O2 oxidation. The performance of the UV oxidation was different depending on the lamp type. The medium pressure lamp showed better performance than the low pressure lamp. Combining the low pressure lamp with hydrogen peroxide (H2O2) improved the removal performance substantially. The by-products formation of tetracycline by UV and UV/H2O2 were investigated. The protonated form ([1 + H]+) of tetracycline was m/z 445, reacted to yield almost exclusively two oxidation by-products by UV and UV/H2O2 oxidation. Their protonated forms of by-products were m/z 461 and m/z 477. The structures of tetracycline’s by-products in UV and UV/H2O2 system were similar.
In this study we followed biofilm formation and development in a granular activated carbon (GAC) filter on pilot-scale during the 12 months of operation. GAC particles and water samples were sampled from four different depths (-5, -25, -50 and –90 cm from surface of GAC bed) and attached biomass were measured with adenosine tri-phosphate (ATP) analysis and heterotrophic plate count (HPC) method. The attached biomass accumulated rapidly on the GAC particles of top layer throughout all levels in the filter during the 160 days (BV 23,000) of operation and maintained a steady-state afterward. During steady-state, biomass (ATP and HPC) concentrations of top layer in the BAC filer were 2.1 μg·ATP/g·GAC and 3.3×108 cells/g·GAC, and 85%, 83% and 99% of the influent total biodegradable dissolved organic carbon (BDOCtotal), BDOCslow and BDOCrapid were removed, respectively. During steady-state process, biomass (ATP and HPC) concentrations of middle layer (-50 cm) and bottom layer (-90 cm) in the BAC filter were increased consistently. Biofilm development (growth rate) proceed highest rate in the top layer of filter (μATP = 0.73 day-1; μHPC = 1,74 day-1) and 78%∼87% slower in the bottom layer (μATP = 0.14 day-1; μHPC = 0.34 day-1). This study shows that the combination of different analytical methods allows detailed quantification of the microbiological activity in drinking water biofilter.
A highly sensitive analytical method based on stir bar sorptive extraction (SBSE) technique and gas chromatography/tandem mass spectrometry (GC/MS-MS) has been developed, allowing the simultaneous multi-analyte determination of seven UV filters in water samples. The stir bar coated with polydimethylsiloxane (PDMS) was added to 40 mL of water sample at pH 3 and stirred at 1,100 rpm for 120 min. Other SBSE parameters (salt effect and presence of organic solvent) were optimised. The method shows good linearity (coefficients > 0.990) and reproducibility (RSD < 12.9%). The extraction efficiencies were above 84% for all the compounds. The limits of detections (LOD) and limits of quantification (LOQ) were 2.1∼8.6 ng/L and 6.8∼27.5 ng/L, respectively. The developed method offers the ability to detect 8 UV filters at ultra-low concentration levels with only 40 mL of sample volume. Matrix effects in tap water, river water, wastewater treatment plant (WWTP) final effluent water and seawater were investigated and it was shown that the method is suitable for the analysis of trace level of 7 UV filters except of benzophenone (BP). The method developed in the present study has the advantage of being rapid, simple, high-sensitive and both user and environmentally friendly.