Utilization of Natural Coagulants in municipal wastewater treatment and comparison analysis study and macrofloc analysis study submitted By Mr. Parth G Manakikar Guided by-Ms. Bhumika Mistry Assistant Professor PGKM’s Haribhai V. Desai College of Arts,Science and Commerce,Pune-02 A Dissertation Submitted to the Dept. of Environmental Science Savitribai Phule Pune University In Partial Fulfillment of the Requirements For the degree of Masters in Environmental Science (M.Sc. Environmental Science) For the year 2019-2020 Through PGKM’s Haribhai V. Desai College of Arts,Science and Commerce,Pune-02 Acknowledgement I thank Haribhai.V.Desai college for providing the various necessary equipment in the research lab and would like to thank my guide Ms.Bhumika Mistry for providing me with the necessary insights and knowledge regarding the topic of my project and would also extend my thanks to the Dept. of Environmental Science for also helping me with my project and last but not the least would like to thank the staff of MITCON labs,Agricultural College dor providing me with some of the above graphs and tabulated data and percentage based data which was utilized in my comparison graphical analysis and for providing me with the floc analysis data even during the pandemic lockdown phase and would also extend my thanks to Mr. Aniket Taware at MITCON food and hygiene lab for providing me with the tabulated parametric analysis data. Declaration I declare that this thesis is an original report of my research, has been written by Parth G manakikar under the guidance of Ms.Bhumika Mistry and has not been submitted for any previous degree. The experimental work is almost entirely my own work; the collaborative contributions of my college H.V. Desai College and MITCON lab has been clearly stated in my report. Certificate This is to certify that the thesis tiled “utilization of natural seed based coagulants in wastewater treatment” has been submitted by Mr. Parth G Manakikar at the Dept of Environmental Science towards partial fulfilment of the requirements for the award of Master’s degree in Environmental Science.This is the Bonafide work of the student. Mr. Pranay Abhang Main Guide Course Coordinator and Asst. Professor Ms. Bhumika Mistry H.V. Desai College Assistant Professor H.V. Desai College Date:10th June 2020 Seal: Index Sr No Title Page No 1) Introduction 1-2 2) Objectives 3-5 3) Material and Methods 6-9 4) Results and Discussion 10- 14 5) Conclusion 15 6) References 19 utilization of natural seed based coagulants in wastewater treatment Parth Manakikar.Ms. Bhumika Mistry Department of Environmental Science,The P.G.KM.s Haribhai V.Desai College,Pune02 Abstract Water is one of the most important and basic human need and nowadays the availability of natural potable/drinkable water is scarce and as most of the treated wastewater is added or released back into the same river which provides water for various domestic purposes and is also utilized as a main source of drinking water and hence when wastewater is treated with the help of synthetic chemical coagulants used especially in the settling tanks during the treatment process and as industrialization increases it results in the degradation of the water quality as it results in the increase in turbidity of the water and decrease in the levels of dissolved oxygen which hence results in smothering of aquatic life in the water and hence degradation of the water body and hence this use of natural seed based coagulant is not only cost effective but are also biodegradable in nature and the sludge formed as a result is less toxic and can be disposed off easily and the treated water contains lesser metalloid toxoids such as aluminium,iron,zinc etc. Moringa olifeira,zea mays,pisum satavium,okra,red kidney beans,black eyed peas and black gram are utilized and the speed of mixing and pH variance and dosage variance is maintained in each and every beaker and hence the RPM variation is vey important for the coagulation and flocculation and precipitation of the various inorganic and organic solids in the wastewater samples. Keywords-Moringa olifeira,zea mays,pisum satavium,red kidney beans,black eyed peas and black gram,optimum speed of mixing,pH variance,dosage variance,coagulation,floculation 1)Introduction My project topic is mostly about the usage of natural plant based coagulants for industrial wastewater treatment. The waster utilized will be mostly grey water form aluminium dye cast industry and the wastewater sample taken will be from an inlet source of the treatment facility before the wastewater is treated in an on-site effluent treatment plant. The use of seeds as natural plant based herbal coagulant is the newest technique in wastewater treatment and can replace the synthetic polymeric chemicals/inorganic chemical in the coming years. The presence of inorganic metalloids in treated wastewater which when released into the environment can pose a lot of problems for the people who depend on that water supply for domestic usage and drinking purposed and as a result there is a steep degradation of the water quality and such dissolved metalloids are proven to have carcinogenic properties resulting in neurotoxicity(Muruganandam et al., 2017) hence such natural treatment method is both useful for the environment and for the populations as a whole as it ensures decline in BOD,COD,TDS and metalloid concentrations in water which will be proven in accordance with comparative analysis study with the help of graphical representation. The dye cast industry wastewater was sampled at the inlet section and the collected wastewater samples were further analysed and the data was collected and analysed with the help of jar test apparataus.The parameters that were analysed were pH, EC,BOD,COD,metal (Muruganandam et al., 2017) concentrations(As,Mn,Pb,Zn,Mg),TSS,TDS,DO and the seeds consisted of Moringa olifeira,zea mays,leguminose seeds such as black gram, red beans and okra seeds and the synthetic polymeric coagulants were aluminium sulphate and poly aluminium chloride(PAC) and hence the varied doses of both the seed extract and the chemical coagulants were added to the wastewater and comparative analysis was done. Macrofloc assessment was also done to find out about the floc strength and floc area and there has been a research gap in this field of microfloc analysis which can help us understand further efficiency of the seed extract in the turbidity removal/reduction. The need for such type of treatment processes is very important in today’s industries as an efficient and cleaner and a more sustainable plant based natural coagulation technique will result in cleaner and less turbid treated water as opposed to the chemicals utilized in the ETP processes in almost every industry nowadays especially automobile industries, metalwork industries. Hence the various safe environmental aspects or significance of this method are mostly the cleaner treatment process,30% turbidity removal was achieved(Balamurugan & Shunmugapriya, 2019) in some research papers and the ability of the natural coagulants to destroy the polymeric monomers which results in less neurotoxic properties of the treated water as due to the efficient bridging process and sweep coagulation hence resulting in an efficient treatment process which shows results. The use of chemical alum is being scrutinized today as it’s continuous use has been linked to many diseases such as Alzheimer’s disease(Engineering & College, 2011) due to its highly toxic sludge production capacity and due to the fact that aluminium remains suspended in the water that has been treated due to the continuous use of chemicals like alum and due to the high turbidity removal efficiency of natural seed based coagulants has been proved to be 21%,83% and 90% in some cases(Choy et al., 2015) and that many seed based coagulants like arachis hypogea are extremely efficient coagulants(Ramesh et al., 2016). 2) Objectives 1) To find out how much optimum dosage is required for efficient treatment process 2) comparing and analysing the efficiency of the natural coagulants utilized 3)To determine the rotations per minute(RPM) while mixing the samples and the optimum natural extract dosage variation 3) Materials and Method The materials required for the experiments mostly consists of beakers,COD digestor,DO bottles,jar test apparataus,stirrer,dried seed extract(oven dried and sun dried),pH meter, conductivity meter(EC),synthetic polymeric coagulants like aluminium sulphate(alum),polyaluminium chloride(PAC),pH buffer tablets to ensure that there is a variance in pH of the different samples The methodology utilized here involves the utilization of coagulation and flocculation at different rpm with the use of jar test apparatus and to mechanically reduce the seeds into powder form and then extracting the powder into water ie. water extraction and then followed by precipitation and sedimentation.The rotation speed is varied for different samples for eg 200 rpm speed and the ph level is optimized in every single sample with the use of pH buffer tablets and after the slow mixing and fast mixing of samples at different rpm and hence most of the parametric analysis for the reduction of BOD,COD,turbity and TSS and TDS shows us the efficiency of the extract and a tabulated data is obtained which indicates the difference in the parametric values and with the usage of the tabulated data many graphical tables can be created which consists of values obtained for the natural extract vs the values obtained for the chemical coagulants and hence the reduction efficiency and other inference can be drawn with regards to the data obtained The next analysis involves the analysis of the flocs or aggregates which also helps in the clear deduction and analysis of the success of the experimentation as macrofloc formation and its characterization is essential in the understanding of the bridge formation mechanism and the research into the efficiency of the aggregation process gives a better understanding of the efficiency of the natural seed based coagulant extract and this analysis is done after the coagulation-flocculation jar test hence the various methodologies involved in the parametric analysis of the wastewater samples prior to the jar testing are the various Indian standard methodologies which are utilized for the metal concentration analysis,BOD,COD,TSS,DO and PH analysis is also done in accordance with these IS methodologies.The natural seed extract is required which consists okra,zea mays,moringa olifeira,pisum satavium,red kidney beans and black gram and is a carefully prepared with the help of a grinder and then this powder extract is filtered and sieved and washed with NaCl and stored in proper airtight containers and the wastewater utilized in this project work is from the PMC wastewater/effluent treatment plant located in shivajinagar and the samples consist of the untreated inlet waster and also the treated outlet water samples are utilized for the analysis of metal concentration reduction along with pH analysis,BOD and COD reduction and the increase/decrease of the dissolved oxygen level in the water will determine if the natural coagulants are efficient or not and the clarity of the water/turbidity removal is also another important parameter which has to be analysed and this is indicated with the help of a line graph,bar graph and a pie chart so as to perform comparative analysis study which is further analysed and the inference/conclusion is reached. The materials required for this study includes a jar test apparataus,pH apparataus,conductivity meter,turbidity meter,14 500ml beakers, whattmans filter paper,pipette,burette,DW,seed extract,synthetic chemical coagulants(PE,PAC,aluminium sulphate or alum,ferric chloride). Filtered and sieved M.Olifeira powder Commented [P1]: Commented [P2R1]: Filtered and seived Okra powder 5)Results and discussion The analysis of the wastewater samples enables us to draw an inference with regards to the potential decrease of tubitdity,dissolved solids,BOD,COD decrease and the increase in the the dissolved oxygen levels and decrease in metalloid concentration and graphical data analysis should give us a clear picture of the toxicity removal efficiency of the seed extract and the amount of dosage required,pH variance required and the various values are indicated in terms of percentage reduction and hence the most efficient seed extract is estimated with the help of graphical comparative analysis and the effect of natural extracts on the pH of the water sample is observed and the increase in acidity or basicity of the samples is also estimated and macrofloc analysis and charecterization is also discussed which gives us the percentage efficiency of the entire process. Table1)Pretreatment data of municipal water samples Tests Municipal water 1) pH 7 2) Hardness(ppm) 285 3) BOD(mg/l) 134.32 4) COD(mg/l) 320.30 5) Turbidity(NTU) 26 6) TSS(mg/l) 228.21 7) TDS(mg/l) 715.75 Table 2) After treatment with Moringa Olifeira Sr Municipal water Tests Dosage 500 mg 200 mg 50 mg 1) pH 7.56 7.49 7.47 2) Hardness(ppm) 238 249 262 3) BOD(mg/l) 61.3 69.16 72.4 4) COD(mg/l) 110.41 135.6 146.3 5) Turbidity(NTU) 21 16 16 6) TSS(mg/l) 46.04 47.8 49.6 7) TDS(mg/L) 174.90 175.94 177.97 Scatter Diagram representing effect of M.Olifeira on Municipal water Bar graph representation of the effect of M.Olifeira on MW Table 3)After treatment with okra Sr No Water Municipal Wastewater Tests Dosage 500mg 200mg 50mg 1) pH 7.66 7.57 7.41 2) Hardness(ppm) 243 251 267 3) BOD(mg/L) 61.3 69.14 72.4 4) COD(mg/L) 88.1 93.3 105.5 5) Turbidity(NTU) 18 21 23 6) TSS(mg/L) 59.6 60.8 67 7) TDS(mg/L) 189.2 191.3 197.3 Effects of Okra on MW 300 250 200 150 100 50 0 0 1 2 3 4 Sr No 5 6 7 8 Water Tests Municipal Wastewater Dosage 500mg Municipal Wastewater Dosage 50mg Municipal Wastewater Dosage 200mg Scatter diagram representing effects of okra on MW over different dosage ranges ie. 50mg,200mg and 500 mg respectively 9 Bar Graph representation showing after treatment effect of municipal wastewater samples with Okra seed powder Effect of Okra on MW 300 250 200 150 100 50 0 1 2 3 4 Sr No 5 6 Municipal Wastewater Dosage 500mg Municipal Wastewater Dosage 50mg Municipal Wastewater Table 4)After Treatment with Alum Sr No 7 Water Tests Water Municipal Wastewater Tests Dosage 500mg 200mg 50mg 1) pH 4.63 5 5.3 2) Hardness(ppm) 240 257 269 3) BOD(mg/L) 36.170 52.156 65.2 4) COD(mg/L) 124.3 140.14 152.20 Dosage 200mg 8 5) Turbidity(NTU) 16 18 20 6) TSS(mg/L) 51.3 52.5 55.8 7) TDS(mg/L) 180.95 184 186 effect of alum on MW at separate dosage 300 250 200 150 100 50 0 pH 1) Hardness(ppm) BOD(mg/L) 2) COD(mg/L) Turbidity(NTU) 4) 5) 3) Municipal Wastewater Dosage 500mg Municipal Wastewater Dosage 50mg Municipal Wastewater TSS(mg/L) TDS(mg/L) 6) 7) Dosage 200mg Bar graph representation of effects of alum on municipal wastewater effect of alum on MW at separate dosage 300 250 200 150 100 50 0 0 1 2 3 Municipal Wastewater Dosage 500mg Municipal Wastewater Dosage 50mg 4 5 Municipal Wastewater 6 7 8 Dosage 200mg Scatter Graph representation of effects of alum at separate dosage 5.1)Effect on pH:from the given table below we can see that the effect on pH with the separate dosage treatment or variance of dosage of M.Olifeira and Okra has no effect of the pH of the municipal wastewater samples and the pH variance of the wastewater was very low with a minimal effect on the readings in the beginning that were obtained and in the case of alum the acidity was found to increase and hence results in the reduction of pH at maximum dosage ie. 500mg and hence more the dosage of alum it results in the excessive presence of aluminium ions in the water which is also one of the root causes for the increase in acidity of the municipal wastewater samples 5.2)BOD removal:M.Olifeira has some reduction properties when it comes to BOD(biological oxygen demand) and as seen from the graphs and tables above we observe that the BOD removal efficiency of M.Olifeira was found to be 48%,50% and respectively at a varied dosage(500mg,200mg and 50mg).Okra as a natural coagulant gives us a removal efficiency of 30%,33%, and as for alum we see BOD reduction of 50%, and 63% respectively.It was hence conclude that when the dosage was increased or varied to a greater extent in terms of mg it resulted in BOD removal at an elevated rate. Graphical representation of BOD reduction in Municipal wastewater for M.Olifeia,Okra and alum respectively for serveral dosage ranges 5.3)COD removal:M.Olifeira has a COD reducing property and the percentage of reduction shows variance in accordance with the several dosage ranges and we get percentage values of COD(chemical oxygen demand) reduction.Hence the values obtained are 52% and 55% COD removal efficiency respectively and for Okra we get 64% and 68% COD removal efficiency whereas alum gives us a removal efficiency of 50% and 49% and hence it is concluded that okra as a natural coagulant gives a better COD reduction efficiency. COD removal efficiency at varying doses 5.4)TDS(total Dissolved solids):It was found that the removal efficiency of the various dissolved solids in the municipal wastewater samples was found to be 74% and 71% for M.Olifeira and foe Okra the reduction efficiency in terms of percentage was found to be 75% and 72.8% respectively and for alum the removal rates are 63% and 70% respectively which indicates that Okra as a natural coagulant is more effective and has a better reduction efficiency in comparison with other natural and synthetic coagulants. 5.5)TSS(total suspended solids):It is hence concluded that the TSS removal efficiency of M.Olifeira is 85% and is significantly higher than the Okra coagulant ie. 70% and 72% respectively whereas the alum removal efficiency of suspended solids was found to be 65% and 71% respectively hence it is concluded in comparison analysis study that solid removal is more efficient with the use of a natural coagulant as opposed to a synthetic polymeric coagulant and hence there is a sure guarantee of utmost purity of the treated municipal water which is then deemed fit for consumption 5.6)Macrfloc analysis:After the process of coagulation and flocculation we have observed that the Macrofloc formation is observed after the addition of natural as well as synthetic coagulants and it is observed that the flocs which are formed as a result of polymeric bridging effect show significant thickness and are closely bound together when natural coagulants are utilized and in the case of M.Olifeira and Okra I observed significant and dense floc formation which indicates that the TDS and TSS removal efficiency of these are very high hence after skimming or removing these flocs significant reduction of dissolved and suspended solids was found in contrst to the synthetic chemical based coagulants like alum and PAC(poly aluminium chloride) the thickess of the flocs and its density was low and scattered flocs were observed and its efficiency was only 65% as opposed to the efficiency of both the natural coagulants which was 72% and 76% resp with okra showing more promise when it comes to dense and tight flocs which are formed. 6)Conclusion As observed from above graphical and tabulated representation which showed that the the removal efficiencies of Natural coagulants which I utilized when it comes to TSS,TDS,BOD,COD,total hardness and the variance of pH in both simulated as well as the municipal waste water from PMC(pune municipal corporation) at several dosage ranges such as 50mg,200mg and 500 mg respectively and the various values that were obtained in the MITCON labs during analysis were duly converted to percentages and the percent conversion showed/indicated better efficiency rates as far as M.Olifiera and Okra seed powders are considered as opposed to synthetic chemical coagulants and further macrofloc analysis study also showed promise as far as efficiency of these natural coagulants and they have a better prospect in the future as we are now more focussed towards environment and the availability of fresh water is also a basic human right which is free from dissolved contaminants and metals and chemicals and it was also found that the aluminium ion concentration was far higher in municipal wastewater treated with the use of chemical coagulants such a as alum and ingestion of these metals which is carcinogenic in nature is not only harmful for the fishes and the various aquatic plants but also for the people who consume this water or utilize it for cooking and bathing purposes. 6)References 1)Choy, S. 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