DEVELOPING ADVANCED CHEMICAL OXIDATION TECHNOLOGY FOR DISINFECTION BYPRODUCT CONTROL OF DRINKING WATER IN SMALL RURAL COMMUNITY

• Sponsoring Institution: National Institute of Food and Agriculture
• Project Status: COMPLETE
• Funding Source: EVANS-ALLEN
• Reporting Frequency: Annual
• Accession No.: 1004422
• Project Start Date: Nov 5, 2014
• Project End Date: Sep 30, 2018
• Program Code: [(N/A)]- (N/A)

Project Director
Yang, JO.

Recipient Organization
LINCOLN UNIVERSITY
820 CHESTNUT ST
JEFFERSON CITY,MO 651023537

Performing Department
Agriculture

Non Technical Summary
It is well known that elevated dissolved organic carbon (DOC) in surface water is a threat to water quality and DOC is the precursor for disinfection byproduct (DBP) formation in drinking water, which has been of environmental and public health concerns. In an effort to safeguard human health in rural community, developing cost-effective technology for controlling DBP formation is urgently needed, especially in small drinking water treatment systems. Fenton or Fenton-like advanced oxidation reactions have been previously used for the degradation of organic contaminants in wastewater treatment and Superfund site remediation. This proposed project is to develop Fenton or Fenton-like advanced oxidation process as an effective strategy to reduce DOC in source water and control carcinogenic DBP formation in drinking water. If successful, results generated from this research will substantially contribute to fundamental understandings of chemical mechanisms on DOC degradation and DBP formation during drinking water treatment and lead to a cost-effective and environmental-safe technology for DBP mitigation in drinking water treatment facilities in rural community. Results would also have greater economic impacts as it will help reduce medical claims by residents consuming drinking water with elevated DBPs and the costs of labor and equipment demand for chlorine handling in drinking water treatment processes.

Animal Health Component

30%

Research Effort Categories

Basic

30%

Applied

30%

Developmental

40%

Classification

Knowledge Area (KA)	Subject of Investigation (SOI)	Field of Science (FOS)	Percent
133	0210	2000	100%

Knowledge Area
133 - Pollution Prevention and Mitigation;

Subject Of Investigation
0210 - Water resources;

Field Of Science
2000 - Chemistry;

Keywords

water quality

drinking water treatment

disinfection byproduct control

human health

Goals / Objectives
Overall goal of this project is to develop cost-effective Fenton and Fenton-like advanced oxidation technology as a practical strategy to control carcinogenic DBPs formation in drinking water and safeguard human health in rural areas, with an integrated approach of laboratory studies and mathematical modeling. Specific objectives include: i) Identifying optimal conditions for the formation of hydroxyl radicals in Fenton process. This task is to systematically investigate the factors that affect the formation of hydroxyl radicals in Fenton process under the conditions relevant to drinking water treatment process. The key parameters that will be investigated include pH, alkalinity, the concentrations of ferrous iron, and the concentrations of DOC.ii) Investigating optimal conditions for the degradation of THM precursors by Fenton process. This task involves the selection of appropriate treatment conditions that are most effective in reducing THM precursors. DOC will be isolated into three to four groups by selective procedures. Each group of DOC will be evaluated in terms of THM formation potential before and after treatment.iii) Developing Fe-GAC catalysts with optimal surface characteristics for THM precursor destruction at circumneutral pH. This task focuses on the preparation and characterization of the Fe-GAC catalysts, including selections of GAC, optimization of iron content and distribution, crystal structure, and surface modification with selected Lewis acids.iv) Identifying major parameters affecting THM precursor destruction in Fenton-like process. This task is to a) probe ?OH generation mechanism through heterogeneous Fenton-like precoess; b) differentiate THM precursor removal pathways and quantify the rates of the corresponding pathways; c) quantify the effects of various parameters affecting the DBP precursor destruction.v) Developing proper strategies for Fe-GAC catalyst regeneration. This task focuses on developing chemical and biochemical approaches for the Fe-GAC catalyst recycling or regeneration.

Project Methods
This study aims to develop a Fenton procedure and heterogeneous catalyst (Fe-GAC) for Fenton-like reaction that could facilitate the destruction of THM precursors. Five tasks will be accomplished following the specified procedures to demonstrate that hydroxyl radical (?OH), generated from Fenton and Fenton-like reactions, could be used as a strong reactant for DOC mitigation and THM control.Tasks i) Identifying optimal conditions for the formation hydroxyl radicals and degradation THM precursors by Fenton process. This task is to systematically assess the factors that affect the formation of hydroxyl radicals in Fenton process under the conditions relevant to drinking water treatment process. Production of hydroxyl radicals will be quantified by the established procedures in literature (Setsukinai et al., 2003; Cohn et al., 2004, 2006; Zhang and Lemley, 2006).The task involves the selection of appropriate treatment conditions that are most effective in THM precursor destruction. The key parameters that will be quantified include pH (5-8), the concentrations of ferrous iron and H2O2 (5-100 mg/L), and the concentration of DOC (2-30 mg/L). Batch kinetic experiments will be carried out in 300-mL flask at ambient temperature in dark. The reaction kinetics will be formulated with appropriate mathematical model.In addition, DOC speciation will be carried out following standard procedures. Each group of DOC will be tested for THM formation potential before and after treatment. THMs will be analyzed by purge and trap gas chromatographic/mass spectrometric method (US EPA method 524.2) after the chlorination of the water sample. The chlorination of the water samples follows a modified Uniform Formation Conditions (UFC) procedure: a) transfer 5.00 mL of the buffered water sample and 35.0 mL buffered DI water (pH 8.0) to the 40 mL incubation vial; b) dose with combined hypochlorite (buffer solution at pH 8.0), cap the incubation vial and invert several times; c) incubate the water at 25ºC in dark for 24 hr. Varian Saturn GC/MS 2000 with a DB-5MS column (J& W Scientific column, I.D 0.25 mm and 60m in length) will be applied for the determination of THMs. The flow rate of the helium carrier gas is set to 1.0 mL/min at 35°C, with inject split ratio of 10 and injector temperature 125°C. Column oven initial temperature is set at 35°C, and then increase to 50°C at 10°C/min and then to 200 at 20°C/min.Task ii) Developing Fe-GAC catalysts with optimal surface characteristics for THM precursor destruction at circumneutral pH.In this task, we will specify the conditions for the preparation of high efficient heterogeneous Fenton catalyst. A variety of Fe-GAC catalysts will be prepared from different oxidative treatments. The preparation will begin by treating GAC sample with Fe(II) at increasing concentrations. Each system will then undergo oxidation under different conditions, yielding a series of iron-impregnated catalysts. The prepared Fe-GAC catalyst will be characterized in terms of Fe content and distribution on GAC, iron crystal structure, surface acidic/basic properties, and specific surface area.Specifically, 2.0 g GAC is added to 200 mL of 0.10 M FeSO4 solution in a 300-mL glass flask, followed by the addition of 10 mL of 1.0 M H2O2 at ambient temperature. The flask is placed on an orbit shaker (Lab-line Instruments Inc.) at 120 rpm to avoid the settlement of the GAC. The pH of the solution is controlled at < 3.5 to prevent Fe(OH)3 precipitation. After 6 hr, the GAC impregnated with Fe(III) is taken out of the flask and washed with Millipore water several times. The catalyst is then dried at 80 °C for 12 hr in oven and 300°C for 2 hr in furnace. The catalysts could be further modified by other Lewis acids such as aluminum chloride to promote iron redox oscillation. To measure the iron content on Fe-GAC, 0.100±0.002 g of Fe-GAC sample is mixed with 30.0 mL of 1:1 HCl, followed by shaking (120 rpm) at ambient temperature for 6 h and then heating in a water bath at 90 ºC for 60 min (Lu, 1995). The supernatant is collected by filtration and the total iron is analyzed by 1,10-phenanthroline spectrophotometric method (APHA, 1989). The crystal structure of iron on Fe-GAC is determined by X-ray diffraction (XRD) analysis. The analysis was conducted with the MiniFlex automated, microprocessor controlled X-ray powder diffractometer, with Cu Kα X-ray source and semiconductor detector, operated at 15 mA and 30 kV.Tasks iii) Identifying major parameters affecting THM precursor destruction in Fenton-like process and Developing proper strategies for Fe-GAC catalyst regeneration. The prepared heterogeneous Fenton catalysts will be assessed for their capability of promoting hydroxyl radical generation from H2O2 at circumneutral pH. The tests will be conducted in stirred batch reactors with water samples collected from Missouri River. Many communities along the Missouri River use the river water as their drinking water supplies. We will evaluate how the major water quality parameters and treatment process could affect THM formation, including water pH, hardness, DOC, dissolved iron in the source water, Fe(III) content on GAC, H2O2 concentration applied, and temperature.A typical kinetic run starts from adding 0.100 g of Fe-GAC to 300 mL glass flask, then transferring 200.0 mL water sample. The flask is covered with aluminum foil to avoid the interference from the room light. After adjusting pH to the desired values with HCl or NaOH, certain amount of H2O2 is spiked at zero time point to initiate the reaction, while Fe-GAC is kept off-bottom with a magnetic stirrer. At fixed time points, 2.0 mL aliquot is withdrawn and filtered through 0.45 mM syringe filter (Fisher Scientific). The fluorescence intensity of filtrate is collected afterwards. All fluorescence measurements will be performed on the Hitachi F-4500 Spectrograph (Hitachi Co.). Samples are held in a standard 1-cm quartz cuvette and the lamp voltage is kept constant at 700 V for all experiments. Fluorescence spectra are collected as EEMS by scanning emission spectra at a range of excitation wavelengths, in which emission spectra are gathered from 250 nm to 550 nm in 3 nm steps, whereas the excitation wavelengths are stepped in 2 nm from 200 nm to 400 nm. The fluorescence scans are performed at a constant room temperature of 23±2°C. The fluorescence intensity is normalized to the water Raman scatter at excitation 248-252 nm/emission 267-273 nm. Selected samples will also be tested for THM formation potentials following the same method as Task ii). In this task, we will evaluate strategies for the recycling and regeneration of used Fe-GAC catalysts and develop a bench-scale pilot treatment system. Eliminating the generation of iron (hydro)oxides sludge in the treatment process could dramatically lower the overall treatment cost, making the process more competitive.

Progress 11/05/14 to 09/30/18

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The PI has mentored one MS graduate student and one undergraduate in environmental science program, as well as one visiting scholar during the project period. The graduate student worked as a graduate research assistant and the undergraduate student as a student assistant. Both students have been trained for research skills and experiential learning on various aspects of proposed research activities, including site sampling, chemical or instrumental analysis, literature review, experimental design and implementation, data processing, reporting, manuscript preparation, as well as conference presentation. The graduate student has successfully completed thesis defense and graduated with MS degree in Environmental Science in Fall 2017. How have the results been disseminated to communities of interest?Publication of research articles, Conference presentations, Classroom lecture. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Results showed that the maximum reduction of DBP formation potential as indicated by total trihalomathanes (TTHMs) would be best accomplished by the combined treatments of H2O2 100 mg/L+1.0 g/L activated carbon (AC) at the presence of 50 mg/L Fe(II), which resulted in a TTHM level below than the regulatory limit by US Environmental Protection Agency (EPA). Data indicated that, with increasing Fe2+ dosage to 0.25 mM, THMs and HAAs after chlorination were substantially reduced from 3,212 μg L-1 and 84 μg L-1 to 188 and 20 μg L-1, respectively, in other words, 94% THMFP and 76% HAAFP reductions through the Fenton treatment. In addition, total organic carbon (TOC) and chemical oxygen demand (COD) also decreased by 30% and 36%, respectively. When [Fe2+] was raised to 0.5 mM, the treatment efficacy would remain relatively same. However, the degradation of dissolved organic matter surrogate (resorcinol) could be significantly improved when dosage of hydrogen peroxide reached at the concentration of 0.25 mM, which could result from accelerated and increased generation of •OH coinciding with the raised dosage of H2O2. This study demonstrated that the concentrations of 0.5 mM [Fe2+] and 0.25 mM H2O2 could achieve a maximum treatment efficacy for reducing THMFP and HAAFP and removing TOC and COD in treated water. The experiments indicated that there were significant removals of THMFP and HAAP at pH 5.0, but under alkaline condition, the formation of ferric oxyhydroxide and the disproportionation reaction of hydrogen peroxide could lower the treatment efficiency. Results also showed that the reduction of THM and HAA forming potentials reached at the highest (92-98%) at a relatively high concentration of resorcinol (12.0 mg L-1). For a similar THMFP and HAAFP removals, it was not necessary to proportionally increase Fenton reagent dosages. As the Fenton reagent dosage increased to a certain level, simultaneous disinfection and DOC removal could be effectively achieved and no detectable E. coli observed in water samples. Experiment also demonstrated that the degradation of H2O2 could be catalyzed by Fe3O4 under the presence of activated carbon (AC) and pH condition similar to drinking water treatment, which would enhance the Fenton or Fenton-like oxidation process for DOC or DBP reduction.

Publications

• Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Rukaria, Paul, John Yang, Bin Hua, Honglan Shi and Enos Innis. 2015. Reducing Disinfection Byproducts in Drinking Water Using Hydrogen Peroxide Oxidation Processes in the Presence of Ferrous Iron. Oral presentation to the 2015 Lincoln University Research Symposium. April 14, 2015. Jefferson City, MO
• Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: John Yang, Paul Rukaria, Bin Hua, Honglan Shi, Enos Innis. 2015. Reducing Disinfection Byproducts in Drinking Water Using Hydrogen Peroxide Oxidation Processes in the presence of Ferrous Iron. Oral presentation to the 2015 Joint Conference of MO-MWEA-AWWA. March 29-April 1, 2015. Osage Beach, MO.
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Almuhanna, A, Hua, B., Yang, J. 2017. Efficacy of Disinfection and Dissolved Organic Matter Reduction in Water by Fenton Reactions. Poster presentation to the 18th ARD Biennial Research Symposium. April 1-4, 2017, Atlanta, GA
• Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Yang, J., Hua, B., Shi, H. 2017. Improving Drinking Water Quality for Selected Rural Communities in Missouri. Poster presentation to the 18th ARD Biennial Research Symposium. April 1-4, 2017, Atlanta, GA
• Type: Journal Articles Status: Published Year Published: 2017 Citation: Runmiao Xue1, Ariel Donovan, Haiting Zhang, John Yang, Bin Hua, Enos Inniss, Yinfa Ma, Craig Adams, Todd Eichholz, Honglan Shi. 2017. Simultaneous Removal of Ammonia and N-Nitrosamine Precursors by Zeolite and Powdered Activated Carbon. J. Env. Sci. doi: 10.1016/j.jes.2017.02.010
• Type: Journal Articles Status: Published Year Published: 2017 Citation: Bin Hua, Huixin Xiong, Mohammed Kadhom, Lei Wang, Guocheng Zhu, John Yang, Gary Cunningham, Baolin Deng.. 2017. Physical-chemical Process of Water Treatment: Overview. Water Environ. Research. Vol 89(10): 974-1028
• Type: Journal Articles Status: Published Year Published: 2018 Citation: Bin Hua, John Yang, Guocheng Zhu, Baolin Deng, Fengjing Liu, Jingdong Mao. 2018. Characterization of Dissolved Organic Matter/Nitrogen Using Fluorescence Excitation-Emission Matrix Spectroscopy and X-ray Photoelectron Spectroscopy for watershed management. Chemosphere 10.1016/j.chemosphere.2018.03
• Type: Journal Articles Status: Published Year Published: 2018 Citation: Runmiao Xue, Yinfa Ma, John Yang, Bin Hua, Enos C Inniss, Craig C Adams, Todd Todd Eichholz. 2018. Evaluation of Thirteen Haloacetic Acids and Ten Trihalomethanes Formation by Peracetic Acid and Chlorine Disinfection. Chemosphere 189(C): 349-356

Progress 10/01/16 to 09/30/17

Outputs
Target Audience:Water treatment operators, rural residents, environmental professionals Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The PI had mentored one MS graduate student during the reporting period. The graduate student worked toward a MS degree as a graduate research assistant and was trained for research skills on various proposed research tasks, including site sampling, chemical or instrumental analysis, literature review, experimental design and implementation, data processing, reporting, manuscript preparation, as well as conference presentation. The student has successfully completed thesis defense and graduated with MS degree in Environmental Science in Summer 2017. How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?We will focus on data analysis, manuscrit writing, and final reporting.

Impacts
What was accomplished under these goals? Our research efforts during the 2016-2017 periods were focused on the batch experiments to systematically investigate the impacts of pH, initial concentration of resorcinol, and the presence of E. coli on TOC, COD, THMPF and HAAFP removal efficiency. Batch experiments were performed in 500-mL reactors stirred by Floc-Tester (ET 740) in the dark at the stirring speed of 100 rpm and reacting temperature of 25 ± 3 oC. The experiments indicated that there were significant removals of THMFP and HAAP at pH 5.0, while under alkaline condition, the formation of ferric oxyhydroxide and the disproportionation reaction of hydrogen peroxide could lower the treatment efficiency. Results also showed that the reduction of THMFP and HAAFP reached at the highest (92-98%) at a relatively high concentration of resorcinol (12.0 mg L-1). For a similar THMFP and HAAFP removals, it was not necessary to proportionally increase Fenton reagent dosages. As the Fenton reagent dosage increased to a certain level, simultaneous disinfection and DOC removal could be effectively achieved and no detectable E. coli observed.

Publications

• Type: Theses/Dissertations Status: Published Year Published: 2017 Citation: Abdulhadi J Almuhanna. 2017. The inactivation of E. Coli and removal of dissolved organic matter in water using hydrogen peroxide by Fenton reactions. MS thesis, Lincoln University of Missouri.

Progress 10/01/15 to 09/30/16

Outputs
Target Audience:Water treatment operators, rural residents, environmental professionals. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The PI has mentored one MS graduate student and one undergraduate in environmental science program, as well as one visiting scholar during the reporting period. The graduate student works toward a MS degree as a graduate research assistant and the undergraduate student works as a student assistant. Both students are trained for research skills and experiential learning on various aspects of proposed research activities, including site sampling, chemical or instrumental analysis, literature review, experimental design and implementation, data processing, reporting, manuscript preparation, as well as conference presentation. How have the results been disseminated to communities of interest?Two journal publications and two conference presentations were made during the reporting period. What do you plan to do during the next reporting period to accomplish the goals?We will continue to work on refiningexperiments to achieve a maximiumtreatment efficacy.

Impacts
What was accomplished under these goals? Our research efforts during the 2015-2016 periods were focused on the batch experiments to investigate the effects of Fe2+ and Fe3+, dosage of Fe2+ and hydrogen peroxide (H2O2), on TOC, COD, THMPF and HAA removal efficiencies of dissolved organic matter surrogate (resorcinol, CAS number 108-46-3). Results indicated that, with increasing Fe2+ dosage to 0.25 mM, THMs and HAAs after chlorination were substantially reduced from 3,212 μg L-1 and 84 μg L-1 to 188 and 20 μg L-1, respectively, meaning 94% THMFP and 76% HAAFP reductions through the Fenton treatment. In comparison with the reduction above, TOC and COD also decreased by 30% and 36%, respectively. When [Fe2+] was raised to 0.5 mM, the treatment efficacy would remain relatively same. However, the degradation of resorcinol could be significantly improved when dosage of hydrogen peroxide was 0.25 mM, which could result from accelerated and increased generation of •OH coinciding with the raised dosage of H2O2. This batch study demonstrated that the concentrations of 0.5 mM [Fe2+] and 0.25 mM H2O2 could achieve a maximum treatment efficacy for reducing THMFP and HAAFP and removing TOC and COD in treated water.

Publications

• Type: Journal Articles Status: Accepted Year Published: 2016 Citation: Hua, B., Shi, H. L., Yang, J., Inniss, E. 2016. Water Quality in Selected Small Drinking Water Systems of Missouri Rural Communities. Beverage doi:10.3390/beverages2020010 Hua, B., Yang, J., Deng, B. L. 2015. Physical-chemical process of water quality. Water Environ. Research. Vol 87(10): 912-945

Progress 11/05/14 to 09/30/15

Outputs
Target Audience:Water treatment operators, rural residents, environmental professionals. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The PI has mentored one MS graduate student and one undergraduate in environmental science program. The graduate student works toward a MS degree as a graduate research assistant and the undergraduate student works as a student assistant. Both students are trained for research skills and experiential learning on various aspects of proposed research activities, including site sampling, chemical or instrumental analysis, literature review, experimental design and implementation, data processing, reporting, manuscript preparation, as well as conference presentation. How have the results been disseminated to communities of interest?Two conference presentations were made during the reporting period. What do you plan to do during the next reporting period to accomplish the goals?We will continue to work on bench experiments to determine the best condition for the most effective treatment.

Impacts
What was accomplished under these goals? Our research efforts during the 2014-2015 periods were focused on 1) investigating the efficacy of the Fenton or Fenton-like advanced oxidation process for reducing dissolved organic carbon (DOC) content, disinfection by-product (DBP) precursors, and DBP formation potential in drinking water, and 2) assessing the degradation of hydrogen peroxide (H2O2) as catalyzed by magnetic iron oxides (Fe3O4). Preliminary results indicated that the maximum reduction of DBP formation potential as indicated by total trihalomathanes (TTHMs) would be best accomplished by the combined treatments of H2O2 100 mg/L+1.0 g/L activated carbon (AC) at the presence of 50 mg/L Fe(II), which resulted in a TTHM level below than the regulatory limit by US Environmental Protection Agency (EPA). Experiment also showed that the degradation of H2O2 could be catalyzed by Fe3O4 under pH condition similar to drinking water treatment, which enhanced the Fenton or Fenton-like oxidation process for DOC or DBP reduction.

Publications