Luận án tiến sĩ: Những đóng góp của Ferdinand Friedrichs vào hệ thống đo lường online độc tố nước thải trên bùn hoạt tính

VIETNAM NATIONAL UNIVERSITY, HANOI VNU UNIVERSITY OF SCIENCE Ferdinand Friedrichs CONTRIBUTIONS TO ONLINE MEASUREMENT SYSTEMS FOR THE INVESTIGATION OF WASTEWATER TOXICITY ON ACTIVATED SLUDGE PH. THESIS IN CHEMISTRY Ha Noi – 2018 LUAN VAN CHAT LUONG download : add luanvanchat@agmail.com VIETNAM NATIONAL UNIVERSITY, HANOI VNU UNIVERSITY OF SCIENCE ------------------------------ Ferdinand Friedrichs CONTRIBUTIONS TO ONLINE MEASUREMENT SYSTEMS FOR THE INVESTIGATION OF WASTEWATER TOXICITY ON ACTIVATED SLUDGE Branch: Environmental Chemistry Code: 62440120 PH. THESIS IN CHEMISTRY Supervisors: Assoc. Do Quang Trung Prof.

Wolfgang Genthe Ha Noi – 2018 LUAN VAN CHAT LUONG download : add luanvanchat@agmail.com Acknowledgement First of all, I would like to thank both of my supervisors, Prof. Genthe who gave me the chance to work for the AKIZ project in Vietnam as an employee of LAR Process Analysers AG, for giving me the chance to work on such an exciting project, any kind of support, inspiring discussions and arranging enough time to finalize the Ph. Many thanks to Prof. Do Quang Trung as my supervisor from the Vietnamese site from Vietnam National University.

I highly appreciate for giving me the opportunity to do my Ph. at the Vietnam National University VNU. Many thanks for the support to finalizing my Ph. subjects, to give me the chance to work on research projects with students from VNU and the interesting discussion related to my Ph.

Secondly, many thanks to all my colleagues at LAR Process Analysers, the AKIZ team, and the members and students from VNU who supported during my time in Vietnam doing my Ph. Special thanks to my lab members Ms. Nhan and Mrs. Lanh for the support in the laboratory and the beautiful time spent together in Can Tho.

Also many thanks to the students from VNU Mr. Dung and Ms. Lanh for coming to Can Tho to do research at the AKIZ laboratory. Many thanks to my colleagues from LAR Process Analysers AG for the support regarding technical issues related to the analysers and the interesting discussion related to the research topic.

Therefore I want to acknowledge Thomas, Rafael, Olga, Olaf, Winfried, Gerhard, and Agnes. Many thanks to the project leader Prof. Rudolph as project leader and Dominic, Rene, Sandra and Mr. Long for coordinating the AKIZ Project.

Last but not least, I would like to thank family and friends for their patience and care, especially to my wife Huyen, my son Nico Tri, and my daughter Lina Kim for keeping me in a good mood. I LUAN VAN CHAT LUONG download : add luanvanchat@agmail.com Declaration I hereby declare that I have written the present thesis independently and without the use of others than the indicated sources. Berlin, 20th June 2017 Signature:____________________ II LUAN VAN CHAT LUONG download : add luanvanchat@agmail.com 1 LUAN VAN CHAT LUONG download : add luanvanchat@agmail.com Acknowledgement First of all, I would like to thank both of my supervisors, Prof. Genthe who gave me the chance to work for the AKIZ project in Vietnam as an employee of LAR Process Analysers AG, for giving me the chance to work on such an exciting project, any kind of support, inspiring discussions and arranging enough time to finalize the Ph.

Many thanks to Prof. Do Quang Trung as my supervisor from the Vietnamese site from Vietnam National University. I highly appreciate for giving me the opportunity to do my Ph. at the Vietnam National University VNU.

Many thanks for the support to finalizing my Ph. subjects, to give me the chance to work on research projects with students from VNU and the interesting discussion related to my Ph. At this point I would like to acknowledge Prof. mult, Rudolph as the leader of the AKIZ project, who always supported me, especially with the publication of scientific articles.

Secondly, many thanks to all my colleagues at LAR Process Analysers, the AKIZ team, and the members and students from VNU who supported during my time in Vietnam doing my Ph. Special thanks to my lab members Ms. Huy and Mrs. Lanh for the support in the laboratory and the beautiful time spent together in Can Tho.

Also many thanks to the students from VNU Mr. Dung and Ms. Hanh for coming to Can Tho to do research at the AKIZ laboratory. Many thanks to my colleagues from LAR Process Analysers AG for the support regarding technical issues related to the analysers and the interesting discussion related to the research topic.

Therefore, I want to acknowledge Thomas, Rafael, Olga, Olaf, Winfried, Gerhard, and Agnes. Many thanks to Dominic, Rene, Sandra and Mr. Long for coordinating the AKIZ Project and their support. Last but not least, I would like to thank family and friends for their patience and care, especially to my wife Huyen, my son Nico Tri, and my daughter Lina Kim for keeping me in a good mood.

Many thanks to my parents who always supported me during my studies and the entire life. I LUAN VAN CHAT LUONG download : add luanvanchat@agmail.com Declaration I hereby declare that I have written the present thesis independently and without the use of others than the indicated sources. Berlin, 16th April 2018 Signature:____________________ II LUAN VAN CHAT LUONG download : add luanvanchat@agmail.com Abstract Removal of nitrogen compounds and organic pollutants from wastewater is one of the essential issues in wastewater treatment. Commonly applied for this treatment step is the activated-sludge process.

To guarantee a proper operation of this process, it is necessary to monitor the inhibitory effect of toxic substances on activated-sludge bacteria. This is commonly done by the activated-sludge respiration-inhibition test. But there is still a lack of knowledge, which parameters have an influence on the stability and sensitivity of the biological test. In the literature, the inhibitory effects of single toxicants on activated sludge may vary up to three orders of magnitudes.

The aim of the study is to increase the sensitivity of toxicants on the activated-sludge respiration test to create an adjustable biosensor. To this end, the research question is as follows: Which parameters have an influence on the sensitivity of the activated-sludge respiration-inhibitions test? The research question is answered through experiments using the international standardized activated-sludge respiration-inhibition test and the two online-respirometers NitriTox and Biomonitor of LAR Process Analysers AG. To influence the sensitivity of these bio assays following parameters were investigated pH, temperature, oxygen concentration in the fermenter, incubation time, nutrient limitation and biomass concentration. These experiments were realized with using Zn(II), Cu(II), Cr(VI) and 3,5 DCP as toxicants.

A series of experiments are described with this objective, and showed in each case, that the sensitivity of the bioassay could be varied by the investigated parameters. The sensitization of the test organisms can be explained by altering the activity of the bacteria and also the speciation of the toxicants in the presence of the nutrient solution and its biological degradation products. It is, therefore, possible to detect toxic pollutants in lower concentrations, which have an inhibiting effect on activated-sludge bacteria. I expect that this new approach is applied to detect inhibiting substances in wastewater in lower concentrations to protect activated-sludge bacteria in a wastewater treatment plant more efficiently.

Additionally, a mobile laboratory was developed and assembled to conduct wastewater monitoring in seven industrial zones across the country Vietnam with toxicity as a critical III LUAN VAN CHAT LUONG download : add luanvanchat@agmail. The aim of the monitoring campaigns was to apply the online respiration inhibition respirometer NitriTox to do a case study in which extend the activated-sludge process of industrial wastewater treatment plant are inhibited by toxic wastewaters in Vietnam. The high necessity of monitoring the toxicity of industrial wastewater can be proved that toxic wastewater occurred in five of the seven tested industrial zones. In conclusion, the NitriTox was applied successfully in the frame of the measurement campaigns in seven industrial zones in Vietnam.

IV LUAN VAN CHAT LUONG download : add luanvanchat@agmail.com LIST OF CONTENTS Acknowledgement. III List of Abbrevations. X List of Figures. XI List of Tables.

The Importance of the Topic. The new Points of this Dissertation. 2 Chapter 1: Literature Review .1 Wastewater Treatment Plant Overview .1 Activated-Sludge Process .1 Inhibition and Toxicity .2 Necessity of Toxicity Monitoring .3 Sum-Parameters in Water Monitoring .4 Sources of Heavy Metal Pollution .5 Toxicity Assessment Methods to Determine the Inhibition of Pollutants on Activated-Sludge Bacteria .6 Activated-Sludge Respiration-Inhibition Test .1 Offline Respiration-Inhibition Measurements .2 Online Respiration-inhibition Measurements .7 Comparison of the Toxicity-Assessment Methods used to determine the Inhibition of Pollutants on Activated-sludge Bacteria .8 Comparison of EC 50 Values of Activated-Sludge Inhibition-Test. 19 V LUAN VAN CHAT LUONG download : add luanvanchat@agmail.3 Influencing Factors on Nitrification-Respiration Inhibition-Test .5 Formation of Toxicant Speciation .7 Growth State of Microorganisms .9 Concentration of the Biomass and Toxins .10 Adaption and Alteration of the Community Structure of Nitrifiers.1 Oxygen-Producing and Oxygen-Consuming Substances .2 pH Change of Substances under Aeration.

33 Chapter 2: Materials and Methods .1 Offline Respiration-Inhibition Measurements .1 International Standard ISO 8192, 2007. Water-Quality test for Inhibition of Oxygen Consumption by Activated-Sludge for Carbonaceous and Ammonium Oxidation (ISO 8192) .2 International Standard ISO 11348-3, 2007. Water-Quality Determination of the Inhibitory Effect of Water Samples on the Light Emission of Vibrio fischeri (Luminescent bacteria test) - Method using Freeze-Dried Bacteria .3 International Standard ISO 9509, 2006. Water-Quality - Toxicity Test for Assessing the Inhibition of Nitrification of Activated-Sludge Microorganisms .2 Online Respiration-Inhibition Measurements .3 Analytical Standard Methods.

46 VI LUAN VAN CHAT LUONG download : add luanvanchat@agmail.4 Toxicity Testing on Real Samples and Standard Solutions .2 Developed Procedure for Toxicity Measurement with the Biomonitor .3 Factors Influencing the Activated-Sludge Respiration-Inhibition Test .4 Influencing Factors to Biomonitor Measurements .1 Influence of Nutrient Solution on Biomonitor Measurements .2 Influence of the sludge concentration on Biomonitor Measurements .3 Influence of the ASR value on Biomonitor Measurements .5 Influencing Factors to NitriTox Measurements.1 NitriTox Measurement According to DIN ISO 8192 .2 Influence of Nutrient Solution on NitriTox Measurements.3 Influence of pH on Inhibition .4 Influence of Temperature on Inhibition .5 Influence of Biomass Concentration on Inhibition .6 Influence of Incubation Time in the Measurement Cell on Inhibition .7 Influence of Incubation Time at the Measurement Phase II on Inhibition .8 Influence of O2 Concentration in the Fermenter on Inhibition .9 Influence of the Sample Matrix Nutrients on Inhibition .6 Toxicants and Standard Solutions.5 Calculation of Theoretical Heavy-Metal Speciation by using MINTEQ 3.6 Technical Introduction of the Mobile Laboratory .7 Inoculum - Nitrosomonas stercoris.3 Activated-Sludge Respiration .4 Rank Scores of Sensitivity.5 Factor of Sensitization. 61 VII LUAN VAN CHAT LUONG download : add luanvanchat@agmail.1 Tra Noc - Industrial Zone .2 Nam Sach - Industrial Zone .3 Hoa Cam - Industrial Zone .4 Hoa Khanh - Industrial Zone .5 Company Groz-Beckert.1 Tra Noc - Industrial Zone .2 Nam Sach - Industrial Zone .3 Hoa Cam - Industrial Zone .4 Hoa Khanh - Industrial Zone .5 Company Groz Beckert .67 Chapter 3: Results and Discussion .1 Studies with the Activated-Sludge Respiration Test Sensitization by Varying Nutrient Solutions .1 Sensitisation of Activated-Sludge Respiration-Inhibition Testing by Varying Nutrient Solutions .2 Influence of the Nutrient Solution on Heavy-Metal Speciation .3 Verifying the Results of Activated-Sludge Respiration-Inhibition Testing using an ORP Electrode .2 Activated-Sludge Respiration Inhibition with the Online Respirometer Biomonitor .3 Validation of Biomonitor Measurements .4 Influencing factors of respiration inhibition with the Biomonitor.1 Influence of Nutrients in the Fermenter .2 Influence of Sludge Concentrations .3 Influence of the ASR value on the respiration inhibition .3 Activated-Sludge Respiration-Inhibition with the Online Respirometer NitriTox. 86 VIII LUAN VAN CHAT LUONG download : add luanvanchat@agmail.1 Validation of NitriTox Measurements .1 NitriTox in-House Round-Robin Test .2 Stability of Results over four Years .3 Comparison of Toxicity-Assessment Methods to Determine the Inhibition of Pollutants on Activated-Sludge Bacteria with the Results of the NitriTox Analyser .4 Comparison of EC 50 Values of Activated-Sludge Inhibition-Test from Literature with NitriTox Measurements .5 NitriTox Measurement according to DIN ISO 8192 .2 Influencing Factors to NitriTox Measurements.1 Influence of Nutrient Solution in the Fermenter .