Chapter 7

Sources and Classification of Water Pollutants

Dr. Vandana

ETZ C362 Environmental pollution Control

BITS Pilani

Outlines
Sources of water pollutants Types of water pollutants and their effects

Two potential sources of water for human use

1. Desalinated sea water or brackish ground water 2. Reclaimed waste water Utilization of water Water resources are developed for irrigation, domestic use, power generation and industrial use

Classification of waste water by their origin

1. Domestic waste water Water discharged from residential and commercial establishments. The pollutants in domestic waste water arise from residential and commercial cleaning operations, laundry, food preparation, body cleaning functions and body excretions. 2. Industrial waste water Discharged from manufacturing plants where water is used for various processes and also for washing and rinsing of equipment, rooms etc. Waste water may be classified as strong, medium or weak depending on the amount of physical , chemical and biological constituents of wastewaters. The constituents of waste water varies from organic solvents, oils, suspended solids to dissolved chemical compounds.

Types of Water pollutants and their effects Water pollutants can be classified into nine categories 1. 2. 3. 4. 5. 6. 7. 8. 9. Oxygen demanding wastes Disease causing agents Synthetic organic compounds Plant nutrients Inorganic chemicals and minerals Sediments Radioactive substances Thermal discharges oil

The value of k1 varies with the type of waste and the temperature.
The methods used to determine the k1 and Lu 1. 2. 3. 4. 5. The least squares method The method of moments The daily difference method The rapid rate method The Thomas method

Why BOD is so important?

Drinking water usually has a BOD of less than 1 mg/l BOD of 3mg/l water is fairly pure BOD of 5mg/l Purity is less

 During the carbonaceous stage, ammonia is produced by the breakdown of organic nitrogen materials.
Ammonia (or ammonium ion) oxidized to nitrite and then to nitrate by Nitrosomonas and Nitrobacter microorganism respctly. 2NH4+ + 3O2 2 NO2- +O2 2NO2- + 2 H2O + 4H+ 2 NO3-

The simultaneous action of deoxygenation and reaeration can be described by the equation, dD/dt = k1L k2D D- dissolved oxygen deficit k1- deoxygenation constant k2 reaeration constant L= Conc. Of the organic material the BOD remaining in time t L = Lue-k1t

D= oxygen deficit in time t D0- initial oxygen deficit at the point of waste discharge
K2,T = reaeration constant at temp. T0C K2,20 =reaeration const.at temp.200C

Effects of other pollutants

BITS Pilani, K K Birla Goa Campus

Pesticides can be classified in to insecticides, herbicides and fungicides.

Sources: Result from surface run off from agricultural lands, waste discharge by pesticide Manufactures and by other means.
Detergents: Active ingredient surfactant or surface active agent. Surfactant lowers the surface tension and allows dirt particles to become linked to the water. The acceptable concentration for surfactants in water is 0.5 ppm. The presence of surfactants reduces the rate of oxygen absorption in water.

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Inorganic chemicals and Minerals Inorganic acids

Inorganic salts
Metal and metal compounds

Inorganic Acids Source: a) b) Mine drainage (mining of sulphur bearing ores containing lead, zinc, copper and iron sulphide (pyrite) Acidic rainfall

Effects: a) b) Acids cause corrosion of metals and concrete Acids are fatal to fish

ET ZC362: Environmental Pollution Control

BITS Pilani, Pilani Campus

Inorganic Salts Source: Industrial effluents, salt from mines or from oil

wells, and ocean salts.

Effects: Salts causes hardness of water Hard water can cause scale formation in pipes, boiler tubes and other industrial equipments

Fatal to fish. Metal Cadmium Source: waste streams from pigment works, textiles, electroplating, chemical plants etc. Permissible Level: 0.01 mg/l (drinking water) Effects: It is not easily detectable in filtered water, particularly if the pH is neutral or alkaline. Itai-Itai disease in Japan was probably due to cadmium
ET ZC362: Environmental Pollution Control BITS Pilani, Pilani Campus

Chromium Source: Waste water of plating operations, paint and dye operation, wastewater from textile, ceramic and glass industry. Permissible level: 0.05 mg/l (Drinking water) Effects: Many plant species are adversely affected by chromium Lead Source: Effluents from battery manufacture, printing, painting. Permissible Level: 0.05 mg/L (Drinking water) Effects: Is a cumulative poison and responsible for cancer.

Mercury
Source: Effluents of Pesticides, Fertilizer Paint and paper, Chlorine industry Permissible Limit : 0.002 mg/l (Drinking water) Effects: Most toxic aquatic pollutant effects on photosynthesis rate.
ET ZC362: Environmental Pollution Control BITS Pilani, Pilani Campus

Silver Source: electroplating and photographic industries. Permissible Limit : 0.05 mg/l (Drinking water) Effects: Cumulative poison and chronic ingestion can cause a permanent discoloration of skin in humans. Fish and lower organisms are susceptible to silver poisoning and silver concentrations of 0.0004 to 0.4 mg/l have proved toxic.

ET ZC362: Environmental Pollution Control

BITS Pilani, Pilani Campus

Sediments Sediments include soil, sand and mineral particles Source: a) b) a) b) By storms and flood waters Deposits of sewage sludge, pulverized coal ash, industrial solids. Pumping equipments, power turbines are affected. Reduces the amount of sunlight, food etc. for water plants, fish and other aquatic bodies.

Effects:

Radioactive substances

Source: Wastes of uranium refining, thorium mining, wastes from nuclear power plants, and from industrial use of radioactive materials.
Effects: Radioactive substances can enter humans with food and water, and get accumulated in blood, and thyroid gland, liver, bone and muscular tissues.
ET ZC362: Environmental Pollution Control BITS Pilani, Pilani Campus

Thermal Discharge

Source:
Power plant industry uses large qualities of water for cooling purposes and directly discharge to water bodies. Consequently, the water temperature is increased, and hot water layer at the top and cold water layer at the bottom are formed. The hot layer denied the oxygen transfer from atmosphere to cold water. Thus, DO levels falls rapidly. And at high temperature the metabolic activity of microorganisms is increased. So, the increase of temperature results to decrease of DO level and to increase of oxygen consumption. Effects:

a)
b)

Cold water fish may dies

An increase in temperature also increases the toxicity of some chemical pollutants.

ET ZC362: Environmental Pollution Control

BITS Pilani, Pilani Campus

Oil
Source: Oil refineries, storage tanks, automobile waste oil, petrochemical plants, tank washing. Effects:

a)

Oil is insoluble in water, it floats and spreads rapidly into a thin layer. This layer can prevent oxygen transfer from the atmosphere, diseases the DO level and creates anaerobic conditions.
At sea, many birds are died by oil slicks.

b)

ET ZC362: Environmental Pollution Control

BITS Pilani, Pilani Campus

ET ZC362: Environmental Pollution Control

BITS Pilani, Pilani Campus

ET ZC362: Environmental Pollution Control

BITS Pilani, Pilani Campus

ET ZC362: Environmental Pollution Control

BITS Pilani, Pilani Campus

Chapter 8

Waste Water Sampling and Analysis

BITS Pilani, K K Birla Goa Campus

Outlines
Learning objectives
Sampling Wastewater analysis

41

Sampling
Two types of samples can be taken : grab sample and composite sample Grab samples: Shows only the prevailing conditions at the time of sampling and are useful in determining the effects of extreme conditions of the waste. Composite sample can be obtained by collecting individual samples at frequent intervals and mixing them together.

Methods of Analysis -Determination of Organic matter

Dissolved Oxygen (DO) Surface waters of good quality should be saturated with DO. Any fall in DO level is one of the first indications that a water body is polluted by organic matter. It is usually determined by Winkler's method", which is based on the reaction of DO with manganese ions to form a precipitate of manganese dioxide.

Manganese dioxide is then treated with iodide ions when iodine is liberated in an amount chemically equivalent to the original DO.

Dissolved Oxygen (DO)

 The interference can also be overcome by using DO analyzers with membrane electrodes. The plastic membrane has the selective ability of allowing oxygen to diffuse through but preventing interfering ions. The DO after diffusing through the membrane, reacts with the metal electrode and causes a cell current which is proportional to the oxygen concentration in the sample. The calibration of the analyzer is done by measuring the DO of a sample of known oxygen content ( determined by Winkler method).

Biochemical Oxygen Demand (BOD)

Most widely used & accepted measure of biodegradable organic content of wastewater is 5-day, 20OC BOD value. Brief analytical procedure is outlined below: 1. Two standard 300-ml BOD bottles are filled completely with the wastewater of which the BOD is to be measured and the bottles are scaled. 2. Oxygen content of one bottle is determined immediately. 3. The other bottle is incubated at 20 oC for 5 days in total darkness, after which its oxygen content is measured 4. The difference between the two DO values is the amount of oxygen that is consumed by microorganisms during the 5 days and is reported as the BOD5 value of the sample.

 The wastewaters may have a high oxygen demand, high enough to deplete all the dissolved oxygen in the sample before the end of 5 days, thus making the test indeterminate. The sample is diluted with high purity water to prevent total depletion of DO. The diluting water is made up of deionized water to which appropriate nutrients, phosphate buffer, trace elements, and seed organisms (usually settled domestic sewage) are added. A blank is run on the diluting water so that the oxygen demand of the same material can be subtracted from the results. The BOD5 is calculated from the following equation:

 When the standard 5-day/20oC conditions are used, approximately two-thirds of the carbonaceous material is broken down; an incubation of about 20 days is needed for nearly complete breakdown. Nitrogenous nutrients can create problems in-the BOD test. However, because of the slowness of the nitrification process, the oxygen demand of the nitrifying bacteria is assumed to be negligible in the standard 5-day incubation period at 20oC. Actual environmental conditions of temp, biological population, oxygen concentration, etc., are impossible to reproduce in the test; hence, care must be taken to extrapolate the test results

 Many industrial wastewaters contain toxic materials which interfere with

the growth of microorganisms thus making the BOD test unreliable. Similarly, the presence of algae in the wastewater affects the BOD test by leading to higher BOD values even when the test is performed in darkness. BOD test is repalced by COD test!!!

Chemical Oxygen Demand (COD)

In the COD test, the oxidizing bacteria of the BOD test are replaced by a strong oxidizing agent under acidic conditions. A sample of the wastewater containing organic material is mixed with an excess of potassium dichromate & sulphuric acid & the mixture is heated under total reflux conditions for a period of 2 hrs. During digestion, the chemically oxidizable organic material reduces a stoichiometrically equivalent amount of dichromate, the remaining dichromate is titrated with standard ferrous ammonium sulphate

 The amount of potassium dichromate reduced gives a measure of the amount of oxidizable organic material. Dichromate has advantages over other oxidants in oxidizing power and applicability to a wide variety of samples. The COD test does not distinguish between organic materials that are biodegradable and those that are not, and, hence, gives a measure of the total oxidizable organic material in the sample. Due to this, the COD test results are higher than those of BOD tests carried out on the same sample.

 If inorganic substances such as chlorides and nitrites are present in the waste water, they interfere with the COD test since they are also oxidized by dichromate Chloride interference can be eliminated by adding mercuric sulphate to the sample prior to the addition of other reagents, and nitrite interference can be overcome by adding sulphamic acid to the di-chromate solution The COD test is much more useful than the BOD test for estimating the oxygen requirements of certain industrial wastewaters.

 It is valuable for wastes where BOD test is not applicable due to the presence of toxic substances, low rate of oxidation, or other similar factors. Ratios of BOD to COD can be employed to get an indication of the degree of biotreatability of the waste. Ratios of 0.8 or higher indicate wastes that arehighly amenable to biological treatment, while lower ratios indicate that the wastes are not favorable to biological treatment.

Total Organic Carbon (TOC)

Total organic carbon test is based - on the oxidation of the carbon of the organic matter to CO2, which is measured by non-dispersive infrared analyzer. Alternatively, the CO2 can be reduced to methane, which is then measured by a FID (Flame Ionisation Detector) In this test, a few micro-litres (5 to 10 ) of the aqueous sample are injected into a combustion tube containing a catalyst & heated to 900oC in a constant flow of air.

 Water is vaporized and the carbonaceous matter is oxidized to CO2. and steam. Outside the combustion tube, the steam is condensed and removed. CO2 is swept into a non-dispersive infrared analyzer, which measures the amount of CO2. The concentration of CO2 is directly proportional to the concentration of total carbon present in the original sample and it includes both organic and inorganic carbon. Inorganic carbon can be measured separately using an acid catalyst at 150oC, which is below the temperature at which organic matter is oxidized.

Schematic diagram of total organic carbon analyser

 Organic carbon content can then be obtained by subtracting the inorganic carbon from the total result. The TOC test can be performed in a relatively short period of time (few minutes) compared to BOD and COD measurements and, hence offers a valuable supplement to BOD and COD estimations. Because of this advantage, an empirical correlation between TOC and COD or BOD, that is specific to a particular plant operation, can be established and from this it is possible to obtain a tentative estimate of the plant performance quickly.

Determination of Inorganic Matters Nitrogen Phosphorus Trace elements Alkalinity

NITROGEN
Major nitrogen species are ammonia, organic nitrogen, nitrites and nitrates. Ammonia (NH3) containing nitrogen & organic nitrogen combindly called Kjeldahl Nitrogen and which contribute ~ 99% of the total nitrogen in domestic waste water. All form of nitrogen can be measured analytically by colorimetric techniques.

Determination of Kjeldahl Nitrogen:

The method comprise with digestion of nitrogen sample with sulfuric acid and catalyst, which decomposes the organic substance by oxidation to liberate the reduced nitrogen as ammonium sulfate. Chemical decomposition of the sample is complete when the medium has become clear and colorless. The solution is then distilled with sodium hydroxide which converts the ammonium salt to ammonia. The amount of ammonia present (hence the amount of nitrogen present in the sample) is determined by several methods like back titration using boric acid and sodium carbonate or using Nessler reagent (potassium mercuric iodide).

MAJOR REACTIONS

Phosphorus
P exists in waste water as orthophosphate, polyphosphate and organic phosphate Orthophosphate is determined by colorimetric method. The sample is treated with ammonium molybdate under acid condition to form molybdophosphoric acid which is then reduced by V/SnCl2 to make color sample. Polyphosphate are first hydrolyzed to orthophosphate and then analyzed. Organic P is first oxidized to phosphate ion & then analyzed

Trace elements and Alkalinity

Major trace elements are: Cr, Pd, Zn Cd Trace elements are determined by AAS & colorimetry. Alkalinity in waste water is due to presence of carbonates, bicarbonates, metal hydroxides. Alkalinity is measured by titrating the sample with N/50 H2SO4 Determination of alkalinity is important in water softening, chemical treatment of waste water, corrosion control, and in removal of ammonia by air stripping.