DETAILED ANALYTICAL METHODS OF THREE DIFFERENT PARAMETERS IN RAW AND SETTLED SEWAGE WATER

An Assignment (CHM 622)

Submitted By ABULUDE, Francis Olawale (M.TECH/SSSE/2010/2736) To

Dr. Olu Jacob Department of Chemistry, School of Science and Science Education, Federal University of Technology, Minna, Niger State.

November, 2011 ABSTRACT

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The importance of water in our daily life makes it imperative that thorough examinations be conducted on it. Examinations conducted are either physical or chemical. The aim of this paper is to provide three detailed analytical methods used for the determination of BOD, COD and Trace metals in raw and settled sewage water samples. In doing this, titrimetric methods are suggested for BOD and COD, while spectrophotometry for trace metals. In both, calculations would be used to obtain the results.

INTRODUCTION Wastewater is any water that has been adversely affected in quality by anthropogenic influence. It comprises liquid waste discharged by domestic residences, commercial properties, industry, and/or agriculture and can encompass a wide range of potential contaminants and concentrations. In the most common usage, it refers to the municipal wastewater that contains a broad spectrum of contaminants resulting from the mixing of wastewaters from different sources (Ademoroti, 1996; FEPA, 2003). Sewage is correctly the subset of wastewater that is contaminated with faeces or urine, but is often used to mean any waste water. "Sewage" includes domestic, municipal, or industrial liquid waste products disposed of, usually via a pipe or sewer or similar structure, sometimes in acesspool emptier. Wastewater treatment as a water use because it is so interconnected with the other uses of water. Much of the water used by homes, industries, and
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businesses must be treated before it is released back to the environment. Wastewater is used water. It includes substances such as human waste, food scraps, oils, soaps and chemicals. In homes, this includes water from sinks, showers, bathtubs, toilets, washing machines and dishwashers. Businesses and industries also contribute their share of used water that must be cleaned. Chemical oxygen demand (COD) is a measure of the capacity of water to consume oxygen during the decomposition of organic matter present in a wastewater sample. COD measurements are commonly made on samples of wastewaters or of natural waters contaminated by domestic or industrial wastes. By COD determination it is possible to quantitatively evaluate organic and inorganic substances which can be oxidized by strong oxidants like K2Cr2O7 in highly acidic solution. Standard dichromate method is often used to measure COD [USEPA, 2001]. The value of COD is always higher than that of BOD because many organic substances can be oxidized chemically but cannot be oxidized biologically. COD represents the total pollution load of the most wastewater discharges [Standard Methods for the Examination of Water and Wastewater, 1997].

Biochemical oxygen demand (BOD) is the measure of the oxygen used by the microorganisms as they decompose the organic matter in the wastewater. It gives an indication of the amount of oxygen needed to biologically oxidize the organic matter present in a wastewater. The current international standard
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for measuring biodegradable organic levels in wastewater is the five-day biochemical oxygen demand (BOD5) [Alexandra et al., accessed 2011, WHO 2003]. The test measures the quantity of dissolved oxygen (DO) consumed by microorganisms during the biological oxidation of organic matter under specified conditions. DO measurements can be conducted by the Winkler iodometric titration method [Standard Methods for the Examination of Water and Wastewater, 1999]. Trace metal testing laboratories detect and identify trace metals content in a wide range of materials and samples (including water samples). Trace metals analysis is available to ppm, ppb and ppt detection levels, depending upon the sample-matrix and technique used. Rapid sample screening to detailed high resolution for detection and measurement of trace metal content is available through the global laboratory network. Trace metal analysis can be applied to trace level detection, identification and quantification testing requirements.

The objective of this paper is to describe in details analytical methods of determination of Biochemical Oxygen Demand (B.O.D.), Chemical Oxygen Demand (COD) and trace metal content of waste water.

EXPERIMENTAL Sample Collection

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Sample containers were thoroughly washed with detergent, rinsed with water and then with distilled water before soaking in 5% HNO3 for about 24hrs. Containers were finally rinsed with distilled water before being used for sampling. Water samples were collected following the procedure recommended by American Public Health Association [1994]. Water and sludge samples were kept cooled en route to the laboratory and stored at 40C while sludge samples were kept frozen at - 180C until analyzed.

Procedure Determination of Biochemical Oxygen Demand (B.O.D.) The following steps should be followed: 1. Place the desired volume of distilled water in a 5 litre flask (usually about 3 litres of distilled water will be needed for each sample). 2. Add 1mL each of phosphate buffer, magnesium sulphate solution, calcium chloride solution and ferric chloride solution for every litre of distilled water. 3. Seed the sample with 12 mL of settled domestic sewage. 4. Saturate the dilution water in the flask by aerating with a supply of clean compressed air for at least 30 minutes. 5. Highly alkaline or acidic samples should be neutralised to pH 7. 6. Destroy the chlorine residual in the sample by keeping the sample exposed to air for 1 to 2 hours or by adding a few mL of sodium sulphite solution.
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7. Take the sample in the required concentrations. The following concentrations are suggested: Strong industrial waste: 0.1, 0.5 and 1 per cent Raw and settled sewage: 1.0, 2.5 and 5 per cent Oxidised effluents: 5, 12.5 and 25 per cent Polluted river water: 25, 50 and 100 per cent 8. Add the required quantity of sample (calculate for 650 mL dilution water the required quantity of sample for a particular concentration) into a 1000 mL measuring cylinder. Add the dilution water up to the 650mL mark. 9. Mix the contents in the measuring cylinder.

10. Add this solution into two B.O.D. bottles, one for incubation and the other for determination of initial dissolved oxygen in the mixture. 11. Prepare in the same manner for other concentrations and for all the other samples. 12. Lastly fill the dilution water alone into two B.O.D. bottles. Keep one for incubation and the other for determination of initial dissolved oxygen. 13. Place the set of bottles to be incubated in a B.O.D. incubator for 5 days at 20C. Care should be taken to maintain the water seal over the bottles throughout the period of incubation. 14. Determine the initial dissolved oxygen contents in the other set of bottles and note down the results.

15. Determine the dissolved oxygen content in the incubated bottles at the end of 5 days and note down the results. 16. Calculate the B.O.D. of the given sample.

Determination of Chemical Oxygen Demand (COD)

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Blend sample if necessary and pipet 50.00 mL into a 500-mL refluxing flask. For samples with a COD of >900 mg O2/L, use a smaller portion diluted to 50.00 mL. Add 1 g HgSO4, several glass beads, and very slowly add 5.0 mL sulfuric acid reagent, with mixing to dissolve HgSO 4. Cool while mixing to avoid possible loss of volatile materials. Add 25.00 mL 0.04167M K2Cr2O7 solution and mix. Attach flask to condenser and turn on cooling water. Add remaining sulfuric acid reagent (70 mL) through open end of condenser. Continue swirling and mixing while adding sulfuric acid reagent.

CAUTION: Mix reflux mixture thoroughly before applying heat to prevent local heating of flask bottom and a possible blowout of flask contents.
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Cover open end of condenser with a small beaker to prevent foreign material from entering refluxing mixture and reflux for 2 h. Cool and wash down condenser with distilled water. Disconnect reflux condenser and dilute mixture to about twice its volume with distilled water. Cool to
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room temperature and titrate excess K2Cr2O7 with FAS, using 0.10 to 0.15 mL (2 to 3 drops) ferroin indicator. 3. Although the quantity of ferroin indicator is not critical, use the same volume for all titrations. Take as the end point of the titration the first sharp color change from blue-green to reddish brown that persists for 1 min or longer. Duplicate determinations should agree within 5% of their average. Samples with suspended solids or components that are slow to oxidize may require additional determinations. The blue-green may reappear. In the same manner, reflux and titrate a blank containing the reagents and a volume of distilled water equal to that of sample.

Calculations: 1. BOD mg/L = (D1 D2) P If concentration is O.1%, then P = (0.1/100 = 0.001) and so on Where D1 = Initial Dissolved Oxygen = ...... mg/L D2 = Dissolved Oxygen at the end of 5 days = ...... mg/L P = Decimal fraction of sample used = ......
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COD (A B) X M X 8000
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COD as mg O2/L = mL sample where: A = mL FAS used for blank, B = mL FAS used for sample, M = molarity of FAS, and 8000 = milliequivalent weight of oxygen X 1000 mL/L.

Trace Metals This can be determined using wet digestion method. Measure a suitable quantity of water sample into 250 ml conical flask. Acidify with 2M HNO3. Swirl to mix. Evaporate to dryness on a steam bath. Cool. Add 25ml conc. HNO3 to the residue in the flask and heat to near boiling. Place it on a hot plate and evaporate the acid to a small volume taking care that there is no spattering in the process. By repeated addition of 25ml conc. HNO3, plus small quantity of H2O2 each time, complete the ashing by repeating the procedure above. When the residue in the flask is white, then the ashing is complete. Add little warm distilled water to the ash obtained and dissolve the ash by adding a minimum amount of conc. HCL. Cool if the resultant solution is hot. Filter using Whatman filter paper No 42. Neutralise the solution with NH4OH. Cool.
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Transfer quantitatively into a suitable volumetric flask and make up to the final mark with distilled water. Calibrate the spectrophotometer according to manufacturers specification. Prepare stock solution, serial dilutions and samples. Run the standards for the working curves. Plot concentration of standard against absorbance. Run the blank to overcome instrumental drift. Then run the samples in triplicates and read the concentration of each sample from the calibration curve.

CONCULSION These approaches to the analyses of COD, BOD and Trace metals in water samples have been shown here to be suitable for the analysis of water samples and the data generated to be of a quality that satisfies the analytical quality requirements. There are other methods which may be used. All that is needed is to consult the reference manuals.

REFERENCES Ademoroti, C.MA (1996): Standard methods for water and effluents analysis. Alexandra Silva, Ricardo J. N. Bettencourt da Silva, M. Filomena G. F. C. Cames. Detailed Evaluation of the Uncertainty for the Determination of Chemical Oxygen Demand in Wastewater.

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http://eurachem2011.fc.ul.pt/presentations/P28-ASilva.pdf (accessed 26/11/2011) APHA (1994): Standard Method for Examination of Water and Waste Water, 18th edn. Washington DC, USA. Fatoki , O. S. and S. Mathabatha (2001): An Assessment of Heavy Metal Pollution in the East London and Port Elizabeth Harbours . Water S. A. 27 (4), 375-380. Federal Government Protection Agency (FEPA), (2003): Guidelines and Standards For Environmental Pollution Control in Nigeria. 238p Standard Methods for the Examination of Water and Wastewater (1997): Chemical Oxygen Demand (COD). Public Health Association,

American Water Works Association, Water Environment Federation. 20th ed., American. Approved by Standard Methods Committee, Standard Methods for the Examination of Water and Wastewater (1999): Biochemical Oxygen Demand (BOD). American Public Health

Association, American Water Works Association, Water Environment Federation. USEPA. Water Quality (2001): Retrieved from www.epa.gov/water science/criteria/wqcriteria WHO (World Health Organization) (2003): Guidelines for Drinking Water Quality. Vol 1. Recommendation WHO. Geneva 130p.

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