ERT 417/4 WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

1. ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011) ‘Characteristics of Industrial Waste’ By; Mrs Hafiza Binti Shukor

2. Student should be able to; EXPLAIN, INTERPRET, and CALCULATE the physical, chemical and biological properties of waste material and DESCRIBE its toxicology. REWRITE the common wastewater constituents and contaminants. ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

3. 4 categories to describe water quality; • Physical • Related to the quality of water for domestic use. • Associated with the appearance of water • Eg. Color, turbidity, temperature, taste and odor. • Chemical • Sometimes evidenced by their observed reactions (comparative performance of hard & soft waters in laundering) • Most often, differences are not visible. • Microbiology • Very important in their relation to public health • Significant in modifying the physical and chemical characteristic of water • Radiological • Considered in areas where there is a possibility that the water may have come in contact with radioactive substances (Davis and Cornwell,2008) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

4. PHYSICAL CHARACTERISTICS • The most important characteristic of wastewater • Composed of floating matter, settleable matter, colloidal matter and matter in solution. • Solids found in wastewater; • Total solids (TS) • Mass remain after evaporation at 103-105oC • Total Suspended Solid (TSS) • Mass remain onwhatman filter GF/C after drying at 103-105oC • Volatile Suspended Solid (VSS) • Solids that can be volatilized and burned off when TSS are ignited at 500+50oC. (applied most commonly to wastewater sludge to measure their biological stability) • Total dissolved solids (TDS) • Those solids that pass through the filter and are then evaporated and dried at specified temp. • Settleable Solids • Solid settle at the bottom of an “Inhoff Cone” after 60mins SOLIDS Solids removed by settling and separated from wash water are calledsludge, which may then be pumped to drying beds or filtered for extraction of additional water (dewatering). ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011) (Metcalf and Eddy, 2003)

5. Continue…. • Measure of the light –transmitting properties of the water due to presence of suspended material such as clay, organic material, plankton & other particulate material. • Measured based on comparison of the intensity of light scattered by reference suspension under the same condition. • Unit = Turbidity Unit (TU)@ • Nephlometric Turbidity Unit (NTU) • Clay @ other suspended particle – not adversely affect health but water containing such particles may require treatment. • Turbidity excess of 5 TU easily detectable in a glass of water. TURBIDITY ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011) (Davis and Cornwell,2008)

6. Continue…. • Refer to degree of absorption of light energy in visible spectrum (400-700nm) • Causes by ; • dissolved organic material from decaying vegetation & certain inorganic matter. • excessive blooms of algae or growth of aquatic microorganisms. • But its presence is aesthetically objectionable & needs • appropriate treatment. • Activated sludge and trickling filters can remove a certain percentage of some types of colored matter. • Sometimes color matters needs chemical oxidation procedures for removal. COLOR ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011) (Davis and Cornwell,2008)

7. Continue…. • Cause by foreign matter (organic compound, inorganic salts @ dissolved gases. • Odors are usually caused by gases produced by the decomposition of organic matter or by substances added to the wastewater. • Industrial wastewater may contain either odorous compounds or compounds that produce odor during the process of wastewater treatment. • Comes from domestic, agricultural @ natural sources. • At point of use, drinking water should be free from any objectionable taste @ odor. TASTE & ODOR ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011) (Davis and Cornwell,2008)

8. Continue…. • Very important parameter - its effect on chemical reactions and reaction rates, aquatic life, and the suitability of the water for beneficial uses. • The increase in the rate of biochemical reactions that accompanies an increase in temperature, combined with the decrease in the quantity of oxygen present in surface waters, can often cause serious depletions in dissolved oxygen concentration in the summer months. • Abnormally high temperatures can foster the growth of undesirable water plants and wastewater fungus • Most desirable drinking waters are consistently cool & do not have fluctuations of more than a few degrees. • Oxygen is less soluble in warm water than in cold water • Industrial establishments that use surface water for cooling-water purposes are particularly concerned with the temperature of the intake water. • Groundwater & surface water usually meet these • criteria. TEMP. ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011) (Davis and Cornwell,2008)

9. Continue…. • The hydrogen-ion concentration is an important quality parameter of wastewater. • The concentration range suitable for the existence of most biological life is quite narrow and critical. • Wastewater with an adverse concentration of hydrogen ion is difficult to treat by biological means, and if the concentration is not altered before discharge, the wastewater effluent may alter the concentration in the natural waters. pH ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011) (Davis and Cornwell,2008)

10. Example 1; Analysis of Solids Data…. Determine the concentration of total solids(TS), total dissolved solids (TDS), total suspended solids (TSS), and volatile suspended solids (VSS) in 50mL of wastewater based on data given; Mass of dry dish = 53.5433 g Mass of dry dish + residue after drying at 105oC = 53.5794 g Mass of dry dish + residue after ignition at 550oC = 53.5625 g Mass of Whatman GF/C filter = 1.5433 g Mass of Whatman GF/C filter + residue after drying at 105oC = 1.5554 g Mass of Whatman GF/C filter + residue after ignition at 550oC = 1.5476 g Ans : Total solids(TS) = 722 mg/L Total dissolved solids (TDS) = 480 mg/L Total suspended solids (TSS) = 242 mg/L Volatile suspended solids (VSS) = 156 mg/L ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

11. CHEMICAL CHARACTERISTICS • Most of water contain. • Amount presence causes by ; • -Leaching of marine sedimentary deposits • -Pollution from sea water @ brine @ industrial @ domestic waste. • Chloride conc. > 250 mg/L – noticeable taste • Domestic water should contain < 100 mg/L chloride. CHLORIDE • Some areas – water source contain natural fluoride. • Excessive fluoride in drinking water – produce fluorosis (mottling) of teeth. • Mottled – black sports @ streaks and may become brittle when exposed to large amounts of fluoride. • Acceptable level for fluoride conc. between 0.8 – 1.3 mg/L FLUORIDE (Davis and Cornwell, 2008) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

12. Nitrogen • Because nitrogen is an essential building block in the synthesis of protein, nitrogen data will be required to evaluate the treatability of wastewater by biological processes. • Insufficient nitrogen can necessitate the addition of nitrogen to make the wastewater treatable. • Where control of alga growth in the receiving water is necessary to protect beneficial uses, removal or reduction of nitrogen in wastewaters prior to discharge may be desirable. • The total nitrogen, as a commonly used parameter, consists of many numerous compounds such as; NH3, NH4-N, NO3-N, NO2-N, urea, organic-N (amines, amino acids, ...etc).

13. Ammonia-Nitrogen Test (Bio Laboratory) • Using DR2800 reactor • Prepare Sample: Fill a 25mL volumetric flask with 25mL of waste sample. • Blank Preparation: Fill a 25mL volumetric flask with 25mL of distilled water. • 3 different reagent (Ammonia Nitrogen Reagent) will be used: • - Mineral Mtabilizer • -Polyvinyl Alcohol • -Nessler Reagent • Add three drops of Mineral Stabilizer to volumetric flask. Stopper and invert several times to mix. • Add three drops of Polyvinyl Alcohol to each volumetric flask. Stopper and invert several times to mix. • Pipette 1.0mL of Nessler Reagent into each volumetric flask. Stopper and invert several times to mix.

14. Phosphorus. • Phosphorus is also essential to the growth of algaeand other biological organisms. • The organically bound phosphorus is an important constituent of industrial wastewater and sludge. Sulfur. • Sulfate is reduced biologically under anaerobic conditions to sulfide, which in turn can combine with hydrogen to form hydrogen sulfide (H2S). • The accumulated H2S can then be oxidized biologically to sulfuric acid, which is corrosive to steel pipes and equipment.

15. Continue…. • Major clases ; • Nitrates (NO3) - • Cyanides (CN) • Heavy metals constituents; • – arsenics (As), barium (Ba), cadmium (Cd), chromium (Cr), lead (Pb), mercury (Hg), selenium (Se), and silver (Ag) • - effects – cause poisons ( As and Cr 6+) • - chronic disease (Pb, Cd, and Hg) TOXIC INORGANIC SUBSTANCES (Davis and Cornwell, 2008) TOXIC ORGANIC SUBSTANCES • There are over 120 toxic organic compounds listed on U.S. Environmental Protection Agency’s Priority Pollutant List. • Eg; pesticide, insecticides and solvents. • Effects may be acute @chronic. (Metcalf and Eddy, 2003) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

16. Continue…. MEASUREMENT OF ORGANIC SUBSTANCES • The analysis used to measure aggregate organic material may be divided into 2; • To measure gross conc. of organic substance greater than 1.0 mg/L • To measure trace conc. in the range of 10-12 to 100 mg/L • Laboratory methods commonly used today to measure gross amounts of organic matter (typically greater than 1mg/L) in wastewater include; • Biochemical oxygen demand (BOD) • Chemical oxygen demand (COD) • Total organic carbon (TOD) • Complementing of these laboratory tests is the theoretical oxygen demand (ThOD), which is determined from the chemical formula of the organic matter. (Metcalf and Eddy, 2003) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

17. Continue…. Biochemical Oxygen Demand(BOD) • The most widely used parameter of organic pollution • 5-day BOD – involved the measurement of the dissolved oxygen used by • microorganisms in the biochemical oxidation of organic matter. • BOD test results are used to; • Determine the appropriate quantity of oxygen that will be required to • biologically stabilize the organic matter present. • Measure the efficiency of some treatment process • Determine the size of waste treatment facilities. • Determine compliance with wastewater discharge permits. • BOD at 20oC for 5 days is used as standard test (measure after 5 days in incubation at 20oC). • Use bacteria to oxidize biodegradable organic in wastewater sample after incubation. • BOD can be calculates by measuring DO before & after incubation. (Metcalf and Eddy, 2003) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

18. Continue…. • BOD can be calculated by; • when the dilution water is not seeded; • BOD (mg/L) = D1 – D2 • P • when the dilution water is seeded; • BOD (mg/L) = (D1-D2)- (B1 – B2) f • P • where, • D1 = dissolved oxygen of diluted sample after preparation (mg/L) • D2 =dissolved oxygen of diluted sample after 5days @ 20oC(mg/L) • P = volumetric fraction of sample used to total volume • B1 = dissolved oxygen of seed control before incubation (mg/L) • B2 = dissolved oxygen of seed control after incubation (mg/L) • f = ratio of sample to seed in control • Seeded is done if the WW is known to contain insufficient numb of microorganism for degradation of WW. • Use suitable bacteria culture with the WW system • CONTROL is used to eliminate effects by the presence of impurities in dilution water to the BOD value (need to aerated atleast 2hr) f = % seed in D1 % seed in B1 (Metcalf and Eddy, 2003) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

19. The limitations of the BOD5 test are as follows: • A high concentration of active, acclimated seed bacteria is required. • Pretreatment is needed when dealing with toxic wastes, and the effects of nitrifying organisms must be reduced. • Only the biodegradable organics are measured. • The test does not have stoichiometric validity after the soluble organic matter present in solution has been used. • An arbitrary, long period of time is required to obtain results.

20. Continue…. REACTION KINETICS OF BOD…. • Is assumed to obey first-order kinetics. integration Where, Lt = amount of 1st order BOD in WW at time t (mg/L) k = reaction rate constant L @ BODL = total @ ultimate carbonaceous BOD (mg/L) • Typical value of k for untreated wastewater (base e) is about 0.23d-1. • 1st order reaction rate constant will be expressed in log (base 10) units. The relationship between k (base e) and K (base 10)is as follows; (Metcalf and Eddy, 2003) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

21. Continue…. REACTION KINETICS OF BOD…. k at temperature (T) other than 20oC, (T = 20 to 30oC) (T = 4 to 20oC) Amount BOD at time t, Amount BOD exertedafter time t, Amount BOD exertedafter 5 days (BOD5), (Metcalf and Eddy, 2003) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

22. Example 2; Calculation of BOD (a) The following information is available for a seeded 5-day BOD test conducted on a wastewater sample. 15mL of the waste sample was added directly into 300mL incubation bottle. The initial DO of the diluted sample was 8.8mg/L and the final DO after 5 days was 1.9mg/L . The corresponding initial and final DO of the seeded dilution water was 9.1 and 7.9 respectively. What is the 5-day BOD (BOD5) of the wastewater sample? Ans : 115.2 mg/L ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

23. Example 3; Calculation of BOD (b) Determine the 1-day BOD and ultimate first-stage BOD for a wastewater whose 5-day 20oC BOD is 200 mg/L. The reaction constant k (base e)=0.23d-1. What would have been the 5-day BOD if the test had been conducted at 25oC? Ans : Lt = 293 mg/L, BOD1=60.1 mg/L BOD5=224 mg/L Example 4; Calculation of BOD (c) If BOD3 for wastewater sample is 75 mg/L and the BOD decay rate constant is k=0.345 day-1, determine the ultimate BOD value. Ans : L = 116 mg/L, ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

24. Example 5; Calculation of BOD (d) A stream of wastewater is discharged into a river at 28oC. What is the fraction of Maximum oxygen usage in 4 days if the BOD rate constant, k which is determined under standard conditions is 0.115 day-1 (assume 0 = 1.135) Ans : K28= 0.317 day-1, BOD4/L=0.72 ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

25. Chemical Oxygen Demand(COD) • To measure degree of oxidation/ degradation of organics using strong chemical agent (dichromate in an acid solution). • measure the organic matter in industrial wastewater that contains compounds that are toxic to biological life. • It oxidizes the reduced compounds in wastewater through a reaction with a mixture of chromic and sulfuric acid at high temperatures. • Measure difference of amount of K2Cr2O7 before and after heating using ferrous ammonium sulfate (FAS) as a reducing agent. • Higher than BOD (because more compounds can be chemically oxidized than can be biologically oxidized) • Ratio BOD/COD varies (usually 1.5: 2 for industrial wastewater containing biodegradable material (e.g. Food Industry). • For wastewaters with ratios higher than 3, it is assumed that some oxidizable material in the sample is not biodegradable. • Nonbiodegradable material sometimes is called refractory and found mainly in wastewater from chemical and pulp & paper industries. (+3) (+6) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011) (Metcalf and Eddy, 2003)

26. CHEMICAL OXYGEN DEMAND (COD) TEST • (BIO LAB) • Use COD reactor (DRB 200). Preheat to 150ºC (2 hours). • Blank Preparation: Use a clean volumetric pipet to add 2.00 mL of distilled water to the vial that contain COD reagent. • Sample Preparation: Use a clean volumetric pipet to add 2.00mL of sample to the vial. • DRB 2800 Spectrophotometer • Reading Method: Select the 435 HR. • Result are in mg/L COD will be displayed.

27. Differences Between Biochemical Oxygen Demand and Chemical Oxygen Demand(COD) (Metcalf and Eddy, 2003) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

28. Total Organic Carbon(TOC) • To determine total organic carbon in an aqueous sample. • The test methods for TOC utilize heat & oxygen, ultraviolet radiation, chemical oxidants, or some combination of these methods to convert organic carbon to carbon dioxide which is measured with an infrared analyzer or by other means. • TOC can be used as a measure of its pollution characteristics and in some cases, it has been possible to relate TOC to BOD and COD values. Theoretical Oxygen Demand (ThOD) • Determined based on ‘chemical formula’ of specific organic substances. • Consider ‘biochemical & nitrogenous oxygen’ demand (Metcalf and Eddy, 2003) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

29. Example 6; Determination of BOD/COD, BOD/TOC, and TOC/COD Ratios Determine the theoretical BOD/COD, BOD/TOC, and TOC/COD ratios for The following compound C5H7NO2. Assume the value of the BOD first-order Reaction rate constant is 0.23/d (base e) (0.10/d base 10) Ans : BOD/COD = 0.68 BOD/TOC = 1.82 TOC/COD = 0.37 ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

30. Example 7; Calculation of ThOD Determine the ThOD for glycine (CH2(NH2)COOH) using the following assumption; a)If the 1st step, the organic carbon & nitrogen are converted to carbon dioxide (CO2) and ammonia (NH3), respectively b)In the 2nd and 3rd steps, the ammonia is oxidized sequentially to nitrite and nitrate. c)The ThOD is the sum of the oxygen required for all three steps. Ans : ThOD= 112 g O2/mol glycine. ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

31. MICROBIOLOGICAL CHARACTERISTICS DISEASE -PRODUCING ORGANISMS (pathogens) • Water for drinking & cooking purposes must be made FREE from disease-producing organisms (pathogens) • Disease-producing organisms (pathogens) – viruses, bacteria, protozoa and helminths (worms). • Some organism can cause disease in people oroginate with the fecal discharge of infected individuals @ animals. • Specific disease-producing organism presence in water are not easily identify. • The techniques for comprehensive bacteriological examination are COMPLEX and TIME CONSUMING. • Eg ; Total Coliform Test (Davis and Cornwell, 2008) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

32. RADIOLOGICAL CHARACTERISTICS • Cause by; • The development and use of atomic energy as a power source • The mining of radioactive materials • Naturally occur • It is necessary to establish limiting concentrations for the intake into the body. • The effect of human exposure to radiation @ radioactive materials are HARMFUL and any unnecessary exposure should be avoided. • The amount of radiation to which the individual is normally exposed varies with the amount of background radioactivity. • Water with high radioactivity is not normal ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

33. Typical range of BOD and S.S. loadfor industrial and municipal wastewater *

34. Important contaminants of concern in industrial wastewater treatment

36. Typical range of concentration values for industrial and municipal wastewater **

37. GENERAL CHARACTERISTICS OF GROUNDWATER & SURFACE WATER Table 1.0 General characteristics of groundwater and surface water Adapted from Davis and Cornwell, 2008 ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

38. GROUNDWATER • Water underneath the ground. • Comes from rain water or water from surface water like lakes or streams that soaks into the soil. • The water is stored underground in the tiny spaces between rocks and soil grains and can move around within the soil. • Groundwater contamination occurs when the water comes into contact with contaminants. ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

39. CHARACTERISTICS OF INDUSTRIAL WASTEWATER • Industrial process generate a wide variety of wastewater pollutant. • The characteristics and level of pollutants very significantly from industry to industry Table 1.1 Example of industrial wastewater concentration for BOD5 and suspended solids (Davis and Cornwell,2008) ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

40. TOXICITY ? • Toxicity is the degree to which a substance is able to damage an exposed organism. • Toxicity can refer to the effect on a whole organism,such as ; • Animal • Bacterium • Plant ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

41. TYPES OF TOXICITY PHYSICAL -include things not usually thought of under the heading of "toxic" by many people -eg. direct blows,concussion, sound and vibration,heat and cold etc CHEMICAL -include inorganic substances such as lead, mercury, asbestos, hydrofluoric acid, and chlorine gas -also organic compounds such as methyl alcohol, most medications, and poisons from living things. BIOLOGICAL -include those bacteria and viruses that are able to induce disease in living organisms. -can be complicated to measure because the "threshold dose" may be a single organism. -Theoretically one virus, bacterium or worm can reproduce to cause a serious infection. ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

42. TOXICITY TEST • Toxicity test are used to; • Assess the suitability of environmental conditions for aquatic life • Establish acceptable receiving water concentrations for conventional • parameter such as DO, pH, temp. or turbidity. • Study the effects of water quality parameters on wastewater toxicity. • Determine the effectiveness of wastewater-treatment method. • Assess the degree of wastewater treatment needed to meet water • pollution control requirement. • Determines compliance with federal & state water quality standard • and water quality criteria. • Establish permissible effluent discharge rate ERT 417/4WASTE TREATMENT IN BIOPROCESS INDUSTRY SEM 1 (2010/2011)

43. NEED FOR INDUSTRIAL WASTEWATER TREATMENT PLANTS Such treatment should comply with the terms of the legislation defining the characteristics of the effluent discharging in water streams. The concept of planning and development should be based on the criteria to protect land, water resources, aquatic life in streams and rivers and marine life from pollution and to safeguard public health as a high priority. The environmental inspection on wastewater treatment plants aims to support and strengthen the Protection of both the environment and the public health, since the pollution generated from the industrial establishments has a negative impact not only on the environment, but also on the health of the individuals. Therefore, it is noted that most of the procedures that could be implemented by industrial establishments to reduce the negative environmental impacts, will also lead to reducing the effects that present a threat to the health of workers within the plants and the public living in regions affected by the various emissions from the plants. In this respect, the effectiveness of the inspection on industrial wastewater treatment plants will lead to the protection of the environment and the protection of workers and public health.

44. THE END…… Thank You