Environmental Pollution and Control III: Water Pollution — Types, Sources and Impacts, Sampling and Analysis of Water Quality Parameters, Microbiological Analysis by MPN, the Indian Drinking Water Standard IS 10500:2012, Drinking Water Treatment, Primary, Secondary and Advanced Wastewater Treatment, and Common Effluent Treatment Plants

This chapter takes the water-pollution item of Unit VI. It covers the types and sources of water pollution and its impacts on people, plants and animals, including the oxygen sag in a river; the sampling and analysis of the parameters the syllabus lists, from pH, conductivity, turbidity and dissolved solids through hardness, chloride and salinity to DO, BOD, COD, nitrate, phosphate, sulphate, heavy metals and organic contaminants; microbiological analysis by the most probable number; the Indian drinking water standard IS 10500:2012; drinking water treatment by coagulation and flocculation, sedimentation, filtration, disinfection and softening; primary, secondary and advanced wastewater treatment; and common effluent treatment plants. Hardness, a surface loading, the food-to-microorganism ratio and the sludge volume index are worked; the underlying chemistry was taught in Unit II.

1. Types and sources of water pollution and their impacts

Water pollutants are conveniently grouped as oxygen-demanding organic wastes (sewage, food-processing and paper-mill effluents), pathogens, plant nutrients (nitrogen and phosphorus, which cause eutrophication), toxic inorganic chemicals (heavy metals, fluoride, arsenic, cyanide), toxic organic chemicals (pesticides, solvents, oil, pharmaceuticals and industrial organics), suspended sediment, heat and radioactive substances. Point sources discharge from an identifiable outlet, such as a sewer or an industrial drain, and can be treated at the end of the pipe; non-point sources, such as agricultural runoff carrying fertilisers and pesticides, urban storm runoff and atmospheric deposition, are diffuse and can be controlled only by changing land use and practice. In India untreated domestic sewage is the largest source of pollution of rivers by volume, because sewage treatment capacity lags behind generation.

The impacts on people are water-borne disease, chronic poisoning by fluoride, arsenic and metals, and methaemoglobinaemia ("blue-baby syndrome") in infants given water high in nitrate, which is why the drinking water limit for nitrate is 45 mg/L as NO₃. For aquatic life the main harm is oxygen depletion: when sewage enters a river, bacteria decompose it and consume oxygen faster than reaeration replaces it, so dissolved oxygen falls downstream to a minimum, the critical point, and then recovers, tracing the oxygen sag curve that Streeter and Phelps modelled in 1925 as a balance between deoxygenation and reaeration. Along the river the zones of degradation, active decomposition and recovery give way to clean water, each with its characteristic organisms. Toxic substances cause fish kills and, through bioaccumulation, contaminate the food chain; nutrients cause algal blooms and eutrophication; and suspended sediment smothers spawning grounds and blocks light for aquatic plants.

2. Sampling and analysis of water quality parameters, and MPN

A grab sample represents one place and moment; a composite sample combines portions taken over time, often in proportion to flow, to represent a day's effluent. Samples must be preserved because many parameters change in storage: dissolved oxygen is fixed on site with the Winkler reagents; samples for metals are acidified with nitric acid; samples for COD and nutrients are acidified with sulphuric acid and cooled to about 4 °C; and BOD samples are cooled and analysed within hours. pH, temperature, conductivity and DO are best measured in the field.

ParameterMethod of analysisSignificance
pH and electrical conductivityGlass electrode; conductivity cell (µS/cm)TDS is roughly 0.55 to 0.7 times EC in µS/cm, a quick field estimate
TurbidityNephelometer measuring light scattered at 90°, in nephelometric turbidity units (NTU)Shields microbes from disinfection; indicates filtration performance
Total dissolved solidsGravimetric: filtrate evaporated and dried at 180 °CTaste; scaling; salinity
HardnessEDTA titration with Eriochrome Black TScale in pipes and boilers; soap consumption
Chloride and salinityMohr's argentometric titration; salinity from chloride or conductivitySaline intrusion, sewage contamination
DO, BOD and CODWinkler or membrane electrode; dilution and incubation; dichromate refluxOxygen status and organic load
Nitrate, phosphate and sulphateUV spectrophotometry at 220 nm or cadmium reduction for nitrate; molybdenum blue (stannous chloride or ascorbic acid) for phosphate; turbidimetry with barium chloride for sulphateEutrophication; blue-baby syndrome; laxative effect and corrosion
Heavy metals and organic contaminantsAAS, ICP-AES or ICP-MS after acid digestion; GC, GC-MS or HPLC after extractionToxicity at very low concentrations

Hardness is caused by divalent cations, chiefly calcium and magnesium. Temporary (carbonate) hardness is due to their bicarbonates and is removed by boiling, which precipitates calcium carbonate; permanent (non-carbonate) hardness is due to their sulphates and chlorides and is not. Hardness is expressed as mg/L of CaCO₃ by multiplying each ion's concentration by the ratio of the equivalent weight of CaCO₃ (50) to its own (20 for Ca²⁺ and about 12.15 for Mg²⁺): hardness = 2.5 × Ca + 4.12 × Mg. Water with 60 mg/L of calcium and 24.3 mg/L of magnesium has a hardness of 150 + 100 = 250 mg/L as CaCO₃, which is hard.

Microbiological quality is judged by indicator organisms. In the multiple-tube fermentation method, portions of the sample, usually five tubes at each of three dilutions, are incubated in lactose broth at 35 °C for 24 to 48 hours; gas production is a positive presumptive test, confirmed in brilliant green lactose bile broth and completed by isolating the organism. The pattern of positive tubes is converted, using tables derived from probability theory, into the most probable number (MPN) of coliforms per 100 mL, a statistical estimate rather than a count. Thermotolerant (faecal) coliforms and E. coli are identified by incubation at 44.5 °C. The membrane filtration method, which filters a measured volume and counts the colonies grown on the membrane, gives a direct count per 100 mL.

3. Indian standards for drinking water: IS 10500:2012

ParameterAcceptable limitPermissible limit in the absence of an alternative source
pH6.5 to 8.5No relaxation
Total dissolved solids500 mg/L2,000 mg/L
Turbidity1 NTU5 NTU
Total hardness (as CaCO₃)200 mg/L600 mg/L
Total alkalinity (as CaCO₃)200 mg/L600 mg/L
Chloride250 mg/L1,000 mg/L
Sulphate200 mg/L400 mg/L
Fluoride1.0 mg/L1.5 mg/L
Nitrate (as NO₃)45 mg/LNo relaxation
Arsenic; lead; cadmium; mercury; total chromium0.01; 0.01; 0.003; 0.001; 0.05 mg/LNo relaxation
Residual free chlorineMinimum 0.2 mg/L1 mg/L
E. coli or thermotolerant coliformsNot detectable in any 100 mL sampleNo relaxation

IS 10500:2012, issued by the Bureau of Indian Standards, sets an acceptable limit and, for some parameters, a higher permissible limit that applies only where no alternative source is available. For toxic substances and for pH, nitrate and bacteriological quality there is no relaxation. Arsenic, as the standard now stands after amendment, is held at 0.01 mg/L without relaxation, the WHO guideline value.

4. Drinking water treatment: coagulation and flocculation, sedimentation and filtration, disinfection and softening

A conventional surface-water treatment plant follows screening and aeration (which releases gases and oxidises iron and manganese) with coagulation, flocculation, sedimentation, filtration and disinfection. Coagulants such as alum are dispersed by rapid mixing and the flocs are grown by slow mixing, with the dose set by jar test. In the clarifier, particles settle if their settling velocity exceeds the surface overflow rate, Q ÷ A, the flow divided by the plan area, typically about 20 to 40 m³/m²/day for flocculated water; a plant treating 10,000 m³/day at 25 m³/m²/day needs 400 m² of settling area, and the tank's depth sets its detention time, V ÷ Q, commonly two to four hours. Slow sand filters run at about 0.1 to 0.2 m/h and purify biologically in the schmutzdecke, needing no coagulation but large areas; rapid sand filters run some thirty times faster, at about 5 m/h, after coagulation, and are cleaned by backwashing.

Disinfection is most often by chlorine. In water chlorine forms hypochlorous acid, HOCl, which dissociates to hypochlorite, OCl⁻, with a pKa of about 7.5; HOCl is roughly 80 to 100 times more effective as a disinfectant, so chlorination works better at lower pH. Chlorine first reacts with reducing substances and with ammonia to form chloramines; beyond the breakpoint, further chlorine appears as free residual chlorine, and breakpoint chlorination ensures a free residual that protects the distribution system, at least 0.2 mg/L at the consumer's tap. Chlorine reacting with natural organic matter forms disinfection by-products such as trihalomethanes, some of them suspected carcinogens; ozone and ultraviolet light are alternatives that leave no residual. Softening removes hardness: in lime-soda softening, lime removes carbonate hardness and magnesium, and soda ash is needed to remove non-carbonate calcium hardness; ion exchange with sodium-form resins or zeolites exchanges calcium and magnesium for sodium; and reverse osmosis removes most dissolved salts.

5. Wastewater treatment: primary, secondary and advanced methods, and common effluent treatment plants

StageUnitsWhat it removes
Preliminary and primaryScreens, grit chambers, oil and grease traps, primary sedimentation tanksFloating material, grit and settleable solids: about 50 to 70% of suspended solids and 25 to 40% of BOD
Secondary (biological)Suspended growth: activated sludge, sequencing batch reactors, aerated lagoons, waste stabilisation ponds; attached growth: trickling filters, rotating biological contactors, moving-bed reactors; anaerobic: upflow anaerobic sludge blanket (UASB) reactorsDissolved and colloidal organic matter, raising total BOD removal to about 85 to 95%
Tertiary or advancedBiological nitrification-denitrification and phosphorus removal, chemical precipitation of phosphate with alum or ferric salts, filtration, activated carbon, membranes (microfiltration, ultrafiltration, reverse osmosis), disinfectionNutrients, residual solids, trace organics, dissolved salts and pathogens, allowing reuse

In the activated sludge process, settled sewage is aerated with a dense suspension of micro-organisms (the mixed liquor), which oxidise the organic matter and flocculate; the mixed liquor then settles in a secondary clarifier, most of the sludge is returned to the aeration tank and the excess is wasted. Two design parameters dominate. The food-to-microorganism ratio, F/M = QS₀ ÷ VX, where Q is the flow, S₀ the influent BOD, V the aeration tank volume and X the mixed liquor suspended solids, is typically 0.2 to 0.4 per day for conventional plants: for Q = 10,000 m³/day, S₀ = 200 mg/L, V = 5,000 m³ and X = 2,500 mg/L, F/M = (10,000 × 200) ÷ (5,000 × 2,500) = 0.16 per day, a lightly loaded plant, with a hydraulic retention time V ÷ Q of 0.5 day, or 12 hours. The sludge volume index, the volume in mL occupied by 1 g of sludge after 30 minutes of settling, SVI = settled volume (mL/L) × 1000 ÷ MLSS (mg/L), measures settleability: 250 mL/L at 2,500 mg/L gives 100 mL/g, good settling, while values above about 150 mL/g indicate bulking, often caused by filamentous bacteria. In India UASB reactors, which treat sewage anaerobically with little energy and produce biogas, and waste stabilisation ponds are widely used where land is available. The sludge from all these processes is thickened, digested, dewatered and disposed of or used on land.

Small and medium industries in industrial estates cannot each afford a treatment plant, so their effluents are collected and treated jointly in a common effluent treatment plant (CETP), supported in India by a central scheme with financial assistance since the early 1990s and run by a special-purpose company of the member units. Each unit must pre-treat its effluent to the CETP's inlet standards so that toxic or incompatible wastes do not upset the biological treatment; the CETP must then meet the discharge standards. The general standards for discharge of effluents into inland surface water under the Environment (Protection) Rules include a BOD of 30 mg/L, a COD of 250 mg/L and suspended solids of 100 mg/L. Where water is scarce or rivers are sensitive, zero liquid discharge, recovering water by evaporation and crystallisation, has been required of some industries.

Key takeaways

  • Water pollutants range from oxygen-demanding wastes, pathogens and nutrients to toxic chemicals, sediment and heat; a sewage discharge produces an oxygen sag with a critical point downstream (Streeter-Phelps).
  • Each parameter has its method: EDTA for hardness, Mohr's titration for chloride, nephelometry for turbidity, molybdenum blue for phosphate, turbidimetry for sulphate, AAS or ICP for metals; hardness as CaCO₃ = 2.5 Ca + 4.12 Mg.
  • MPN estimates coliforms per 100 mL statistically from multiple-tube fermentation; IS 10500:2012 allows no E. coli in 100 mL, sets pH 6.5 to 8.5, fluoride 1.0 (1.5), nitrate 45 and arsenic 0.01 mg/L.
  • Drinking water is coagulated, settled (overflow rate Q ÷ A), filtered (slow or rapid sand), chlorinated beyond the breakpoint (HOCl works best below pH 7.5) and softened by lime-soda or ion exchange.
  • Wastewater passes primary, secondary (activated sludge, trickling filter, UASB) and tertiary treatment; F/M = QS₀ ÷ VX and SVI above about 150 mL/g signals bulking; CETPs treat the joint effluent of small industries.

Practice questions (10)

Attempt each one before opening the answer. Every explanation names the tempting wrong option as well as the right one, because that is where marks are lost.

  1. A water sample contains 60 mg/L of calcium and 24.3 mg/L of magnesium. Taking the conversion factors as 2.5 for calcium and 100/24.3 for magnesium, what is its total hardness in mg/L as CaCO₃?

    Numerical answer — type the value.

    Show answer

    Answer: 250

    Calcium contributes 60 × 2.5 = 150 mg/L and magnesium 24.3 × (100 ÷ 24.3) = 100 mg/L as CaCO₃, so total hardness is 250 mg/L. Simply adding 60 and 24.3 gives the ions' own mass, not hardness expressed as CaCO₃.
  2. An activated sludge plant treats 10,000 m³/day of settled sewage with a BOD of 200 mg/L in an aeration tank of 5,000 m³ holding 2,500 mg/L of mixed liquor suspended solids. What is the food-to-microorganism ratio per day, to two decimal places?

    Numerical answer — type the value.

    Show answer

    Answer: 0.16

    F/M = QS₀ ÷ VX = (10,000 × 200) ÷ (5,000 × 2,500) = 2,000,000 ÷ 12,500,000 = 0.16 per day. The concentration units cancel, leaving per day; the hydraulic retention time of this tank is V ÷ Q = 0.5 day, a separate quantity.
  3. Chlorination is more effective at pH 6.5 than at pH 9 because at lower pH

    1. more chloramines are formed
    2. chlorine gas escapes more slowly
    3. bacteria reproduce more slowly in acid water
    4. more of the chlorine is present as hypochlorous acid, which is a far stronger disinfectant than hypochlorite
    Show answer

    Answer: D — more of the chlorine is present as hypochlorous acid, which is a far stronger disinfectant than hypochlorite

    HOCl ⇌ H⁺ + OCl⁻ has a pKa of about 7.5, so below it HOCl dominates, and HOCl, being uncharged, penetrates cell walls and is roughly 80 to 100 times more germicidal than OCl⁻. Chloramines are weaker disinfectants than free chlorine, not stronger.
  4. For which of the following parameters does IS 10500:2012 allow no relaxation beyond the acceptable limit? Select all that apply.

    1. Lead (0.01 mg/L)
    2. pH (6.5 to 8.5)
    3. Total dissolved solids (500 mg/L)
    4. Nitrate (45 mg/L)
    Show answer

    Answer: A — Lead (0.01 mg/L); B — pH (6.5 to 8.5); D — Nitrate (45 mg/L)

    pH, nitrate and toxic metals such as lead have no relaxation. TDS has an acceptable limit of 500 mg/L but may be relaxed to 2,000 mg/L where no alternative source exists, because high TDS affects taste more than health.
  5. Temporary hardness of water is caused by

    1. sodium chloride
    2. sulphates and chlorides of calcium and magnesium
    3. dissolved carbon dioxide alone
    4. bicarbonates of calcium and magnesium, and is removed by boiling
    Show answer

    Answer: D — bicarbonates of calcium and magnesium, and is removed by boiling

    Boiling decomposes bicarbonates and precipitates calcium carbonate, removing carbonate (temporary) hardness. Sulphates and chlorides give permanent (non-carbonate) hardness, and sodium does not cause hardness at all, because hardness is due to divalent ions.
  6. Assertion (A): In lime-soda softening, soda ash must be added to remove non-carbonate calcium hardness. Reason (R): Lime alone precipitates calcium only in proportion to the bicarbonate present, so calcium balanced by sulphate or chloride stays in solution. Choose the correct option.

    1. Both A and R are true, and R is the correct explanation of A
    2. Both A and R are true, but R is not the correct explanation of A
    3. A is true, but R is false
    4. A is false, but R is true
    Show answer

    Answer: A — Both A and R are true, and R is the correct explanation of A

    Both are true and R explains A. Lime converts bicarbonate to carbonate, which precipitates CaCO₃, but calcium associated with sulphate or chloride has no carbonate to precipitate with; soda ash, Na₂CO₃, supplies that carbonate, leaving soluble sodium salts.
  7. The most probable number (MPN) test is used to estimate

    1. the biochemical oxygen demand
    2. the turbidity of water
    3. the number of coliform bacteria per 100 mL of water
    4. the concentration of heavy metals
    Show answer

    Answer: C — the number of coliform bacteria per 100 mL of water

    MPN uses multiple-tube fermentation in lactose broth and probability tables to estimate coliforms per 100 mL, the standard index of faecal contamination. BOD is an oxygen-demand test, and metals and turbidity are measured instrumentally.
  8. Which of the following are secondary (biological) wastewater treatment processes? Select all that apply.

    1. Breakpoint chlorination
    2. Activated sludge process
    3. Screening
    4. Trickling filter
    Show answer

    Answer: B — Activated sludge process; D — Trickling filter

    Activated sludge (suspended growth) and trickling filters (attached growth) use micro-organisms to oxidise dissolved organic matter. Screening is a preliminary physical step, and breakpoint chlorination is disinfection, part of tertiary treatment.
  9. A mixed liquor sample with 2,500 mg/L of suspended solids settles to 250 mL/L in 30 minutes. Its sludge volume index and settling behaviour are

    1. 100 mL/g, indicating good settling
    2. 0.1 mL/g, indicating rising sludge
    3. 10 mL/g, indicating bulking
    4. 1,000 mL/g, indicating good settling
    Show answer

    Answer: A — 100 mL/g, indicating good settling

    SVI = settled volume (mL/L) × 1000 ÷ MLSS (mg/L) = 250 × 1000 ÷ 2500 = 100 mL/g, within the good range of about 50 to 150. Bulking sludge settles poorly and gives SVIs above about 150 mL/g, not low values.
  10. Under IS 10500:2012 the acceptable limit for fluoride in drinking water, and the permissible limit in the absence of an alternative source, are

    1. 0.5 mg/L and 1.0 mg/L
    2. 1.0 mg/L and 1.5 mg/L
    3. 45 mg/L with no relaxation
    4. 1.5 mg/L and 3.0 mg/L
    Show answer

    Answer: B — 1.0 mg/L and 1.5 mg/L

    Fluoride is 1.0 mg/L acceptable and 1.5 mg/L permissible; above that, dental and skeletal fluorosis become common. 45 mg/L with no relaxation is the nitrate standard.