3.3.

2 Water Analysis Methods

3.3.2.1 Field tests

Groundwater samples were analyzed in the field for pH, Eh, Electrical Conductivity (EC),
Dissolved Oxygen (DO) and Temperature measurements. A Jenway combined pH/Conductivity
meter Model 430, was used for pH, Eh, Conductivity and Temperature measurements whereas
HANNA model HI 9142 meter was used for Dissolved Oxygen measurements, respectively in
the field. Standards used were Jenway pH buffers at 4.00, 7.00 and 10.1, Jenway 1413 µ S/cm
conductivity standard; and HANNA zero oxygen solution. Each day, the pH probe was
recalibrated using a 2 point calibration, the EC probe and DO meter were also calibrated every
morning.

To measure pH, Eh, EC, DO and Temperature on site in the field, respective probes
were rinsed with deionized water and blot dried. A 50 ml beaker was first rinsed with deionized
water then with groundwater to be sampled in order to reduce cross-contamination. The beaker
was then filled with sample, the probes placed in it and a stable reading was noted in the field
book.

Depth of wells was determined by a rope used for fetching groundwater from wells and
was prior marked in feet accordingly. Water level of each well was determined by asking over to
well owners. However most of the wells in the study area are dug-well type and a standard dug-
well is basically a hole, with a diameter of 1 meter and depth of maximum 3-4 feet below the
water table or even less and may possibly be dug deeper than 3 to 4 feet below the water table.

3.3.2.2 Major Ion Analyses

3.3.2.2.1 Determination of CALCIUM by EDTA titration using Murexide as indicator
3.3.2.2.1.1 Solution preparation

• Standard Calcium carbonate solution (1000 ppm): Dissolved 0.1 g anhydrous CaCO3
powder in 100 ml volumetric flask with little deionized water and 0.5 to 1 ml of HCl was
slowly added for digestion until all the CaCO3 was dissolved and volume made up to mark
with deionized water. This standard solution was equivalent to 1 mg CaCO3 or 0.4008 mg
Ca / 1 ml EDTA (B Factor).

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• Standard EDTA titrant solution (0.01M): Dissolved 3.724 g EDTA sodium salt in little
deionized water and diluted up to 1 liter. This solution was standardized against standard
calcium carbonate solution. Exactly 0.01M of this solution was equivalent to 0.4008
mg Ca / 1ml EDTA.

• Murexide indicator solution: As aqueous solution of murexide is unstable, however

ground mixture of dye powder and sodium chloride (NaCl) provides a stable form of the
indicator. Therefore solid indicator mixture was prepared by mixing 200 mg murexide with
100 g solid NaCl and grinded to 40-50 mesh. Approximately 0.2 g of this solid indicator
mixture was used for titration.

• Sodium hydroxide solution (1M): Dissolved 40 g sodium hydroxide pellets in 1000 ml

beaker with little deionized water and volume made up to mark.

3.3.2.2.1.2 Procedure

To each 25 ml of the samples, 2 ml of 1M NaOH solution was added to attain pH 12 to

13. To this solution, 2 to 3 drops of murexide indicator were added and titrated immediately,
because murexide is unstable under alkaline conditions. Titration was carried out slowly with
0.01M EDTA standard solution. with continuous stirring using 10 ml burette to produce the
proper end point from red to blue violet. Checked the end point by adding 1 to 2 drops of EDTA
in excess to make certain that no further change in color appeared (Clesceri et al., 1998).

3.3.2.2.1.3 Calculation

Calcium (mg/L) = A x B x 0.4008 x 1000 / vol. of sample taken

Whereas, A = ml of EDTA consumed, B = mg CaCO3 equivalent to 1ml EDTA titrant at the

indicator end point. If, EDTA standard solution was exactly equivalent to 1 mg CaCO 3 per 1 ml
EDTA, then omitted ‘B’ from equation. Factor 0.4008 = Equivalent weight of calcium.

3.3.2.2.2 Determination of MAGNESIUM by EDTA titration using EBT as indicator

3.3.2.2.2.1 Solution Preparation

• EDTA standard solution (0.01M): Same as prepared for Section 4.2.2.2.1.1.

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 • Ammonia buffer solution (pH=10): Dissolved 70 g NH4Cl in 570 ml of NH3 solution and
volume was made up to 1000 ml with deionized water.

• Eriochrome Black T indicator: 0.4 percent (0.1 g EBT dyestuff / 25 ml methanol)

solution of the pure dyestuff was prepared in methanol. This solution remains workable for
at least a month.

3.3.2.2.2.2 Procedure

To each of 25 ml samples, 4 ml of ammonia buffer solution was added to maintain pH of

10 ± 0.1 units during titration. To this solution, 2-3 drops of EBT indicator were added and the
solution was titrated slowly with 0.01M standard EDTA solution using 10 ml burette with
continuous stirring to the proper end point. Appearance of sky blue color and disappearance of
the last reddish tinge identified the end point (Clesceri et al., 1998; Best and Ross, 1977).

Note: Titration using EBT indicator gives the total calcium and magnesium hardness. By
subtracting the volume used for calcium in section 4.2.2.2.1.2, magnesium contents can be
calculated.

3.3.2.2.2.3 Calculation

Magnesium (mg/L) = A x B x 0.2440 x 1000 / vol. of sample taken

Whereas, A = ml of EDTA used for titration, which can be determined by A = (Y – Z)

whereas, Y = ml of EDTA used for Ca and Mg, Z= ml of EDTA used for
Ca alone.

B = mg CaCO3 equivalent to 1 ml EDTA titrant at the calcium indicator end point.

Factor 0.2440 = Equivalent weight of magnesium ion.

Note: Generally hardness is expressed in terms of an equivalent amount of CaCO3, hardness

and is calculated by adding the milliequivalents of Ca and Mg per liter and multiplying the sum
by 50. meq/L of Ca and Mg are calculated by dividing mg/L values of these ions by their
equivalent weights.

Conversion method: Milliequivalents of Ca = mg/L of Ca / 20

Milliequivalents of Mg = mg/L of Mg / 12
Hardness as CaCO3 = Sum of milliequivalents of Ca and Mg x 50

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3.3.2.2.3 Determination of Carbonate and Bicarbonate titrimetrically
3.3.2.2.3.1 Solution preparation

• Sodium carbonate standard solution (0.01N): (For standardization of HCl solution)

Dissolved 1.767 g Na2CO3 in 1 liter of deionized water. Exactly 1 ml of this solution

corresponds to 2 ml of 0.01N HCl solution.

• HCl solution (0.121N): 10 ml of 37% HCl was added in little deionized water to make a
total volume of 1 liter with deionized water.

• HCl (0.01N) working standard solution: 82.65 ml of 0.121N HCl stock solution was
diluted with little deionized water to make a total volume of 1 liter with deionized water. This
solution was used for titration.

• Phenolphthalein indicator solution: Prepared 0.5% w/v in 50% v/v industrial

methylated spirit.

• Bromocresol green indicator solution: Prepared 0.5% w/v in deionized water.

3.3.2.2.3.2 Procedure

Titration of water samples having pH greater than 8.3 (as carbonate ions exist only at
pH >8.3) was done with 0.01N HCl standard solution, using phenolphthalein and bromocresol
green as indicator in two steps and the amount of carbonate and bicarbonate was calculated by
difference method. Other wise, for sample having pH values less than 8.3, titration was done
directly with 0.01N HCl standard solution using bromocresol green indicator.

To each 25 ml of water sample, few drops of phenolphthalein indicator were added. The
solution was titrated until the pink color disappeared and the burette reading was recorded as P
ml. The pink color indicates the presence of carbonate ions.

To the same colorless solution 2-3 drops of bromocresol green indicator were added and
the titration was continued until the blue color changed to green. The burette reading was
recorded as T ml, where T is the total volume of acid including P (Clesceri et al., 1998).

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3.3.2.2.3.3 Calculations

The volume consumed for carbonate and bicarbonate was calculated as follows;

Carbonate: CO32- = 2 (P ml)

Bicarbonate: HCO3- = T ml - 2 (P ml)

Now substitute these volumes into formula,

Carbonate (mg/L) = A x B x 30 x 1000 / vol. of sample taken

Bicarbonate (mg/L) = A x B x 61 x 1000 / vol. of sample taken

Whereas, A= Volume of acid used for titration; B = Normality of acid; 30, 61 = Equivalent
weights of carbonate and bicarbonate ions respectively.

Note: Like hardness alkalinity can be expressed in terms of CaCO3 and is calculated as

Conversion method: Milliequivalents of Carbonate = mg/L of CO32- / 30

Milliequivalents of Bicarbonate = mg/L of HCO3- / 61
Alkalinity as CaCO3 = Sum of milliequivalents of CO3-2 and HCO3- x 50

3.3.2.2.4 Determination of CHLORIDE ions titrimetrically with silver nitrate solution using
potassium chromate as indicator

3.3.2.2.4.1 Solution Preparation

• Silver nitrate solution (0.1N): 16.986 g of silver nitrate (AgNO3) was dissolved in
deionized water and volume made up to 1 liter. This solution was standardized against 0.1N
NaCl, exactly 1 ml of 0.1N AgNO3 solution correspond to 1 ml of NaCl solution. This solution
was used for determination of chloride ions in high TDS water.

• Silver nitrate solution (0.01N): Prepared by diluting 100 ml of 0.1N silver nitrate
solution in little deionized water and volume was made up to 1 liter with the same. This
solution was used as working solution for determination of chloride ions in low TDS water
samples.

86
 • Sodium chloride solution (0.1N): 5.85 g of NaCl was dissolved in little deionized water
and the volume was made up to 1 liter with the same.

• Potassium Chromate indicator (5 %): 5 g of potassium chromate (K2CrO4) was

dissolved in little deionized water. Few ml of silver nitrate solution was added until a definite
red precipitate was formed. This solution was left for 12 hours, filtered and diluted to 100 ml
with deionized water.

3.3.2.2.4.2 Procedure

To each 25 ml of water sample few drops of potassium chromate indicator were added
in 100 ml conical flask. Titration of samples was done with 0.01N silver nitrate solution until the
color just changed from yellow to orange-red (Clesceri et al., 1998; Best ad Ross, 1977).

3.3.2.2.4.3 Calculation

Chloride (mg/L) = (A-B) x N x 35.45 x 1000 / vol. of sample taken

Whereas, A = Volume of silver nitrate solution consumed (ml) for titration, B = Volume of silver
nitrate solution consumed (ml) for blank, N = Normality of silver nitrate solution, Factor
35.45 = Equivalent weight of chloride ion, 1000 = to convert results into per liter.

3.3.2.2.5 Determination of SODIUM and POTASSIUM ions using Flame photometer

3.3.2.2.5.1 Solution preparation

• Sodium stock solution (1000 mg/L): 2.543 g of NaCl was dissolved in little deionized
water and the volume was made up to 1 liter with deionized water.

• Sodium standard solutions for calibration: A series of 10, 20, 30, 40, 50, 60, 70, 80,
90, and 100 mg/L Na standard solutions were prepared by diluting appropriate amount of
1000 ppm Na standard solution with little deionized water in 100 ml volumetric flasks and
volume was made up to mark with deionized water. These standard solutions were used for
the construction of calibration curve.

• Potassium stock solution (1000 mg/L): 1.91 g of KCl was dissolved in 1000 ml
volumetric flask with little deionized water and the mark was filled with the deionized water.

87
• Potassium standard solutions for Calibration: Similarly a series of 10, 20, 30, 40, 50,
60, 70, 80, 90, and 100 mg/L K standard solutions were prepared by diluting correct amount
of 1000 ppm K standard solution with little deionized water in 100 ml volumetric flasks and
volume was made up to mark with deionized water. These standard solutions were used for
the construction of calibration curve.

3.3.2.2.5.2 Procedure

By introducing 100 mg/L sodium standard solution, flame photometer (Corning, Model
410) read out knob was set at 100 till constant reading. Now series of sodium standard solutions
was simultaneously run in the concentration range. The calibration curve of sodium for
concentration versus emission intensity was obtained. Concentration of unknown was
calculated from calibration curve in the linearity range of sodium standards solutions. Samples
with high concentrations were diluted with deionized water within the concentration range of
calibration curve and multiplied with the sodium values determined with calibration curve.
Similar procedure was adopted to determine potassium ions (Clesceri et al., 1998).

3.3.2.2.6 Determination of FLUORIDE ions by Ion Selective Electrode method

3.3.2.2.6.1 Solution preparation

• Fluoride Standard solution (100 mg/L): Prepared by dissolving 0.221 g anhydrous

NaF in little deionized water in 1 liter volumetric flask and the volume was made up to mark
with deionized water.

• Fluoride working standard solutions: Prepared 1 and 10 mg/L F- working standard

solutions from 10 mg/L F- standard solution respectively in 100 ml volumetric flasks with
deionized water.

• Complexing and buffer solution (TISAB): To approximately 500 ml deionized water in

1000 ml beaker, added and dissolved 84 ml conc. HCl (36-38 %), 242 g TRIS
(hydroxymethy amino methane) and 230 g sodium tartrate (Na2C4H4O6 . 2H2O). Cooled to
room temperature and transferred to a 1000 ml volumetric flask and diluted to mark with
deionized water.

3.3.2.2.6.2 Procedure

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 Ion meter (Orion, model 710A) was adjusted at relative millivolt mode. In order to
determine the slope of electrode transferred 25 ml of 10 mg/L F- standard solution into 100 ml
polypropylene beaker, added 25 ml of TISAB and a magnetic bar. Immersed both, reference
and fluoride ion selective electrodes into solution and measured developed potential while
stirring on a magnetic stirrer. Electrodes were kept in the solution until the reading was constant
at 0 mV. Electrodes were rinsed with deionized water and blot dried. Similarly 1 mg/L F -
standard solution was treated until constant reading at 56 ± 2 mV. Plotted potential
-
measurements of F standards against concentration on two-cycle semi logarithmic graph
paper. Plotted milligrams F- per liter on the logarithmic axis (ordinate), with the lowest
concentration at the bottom of the graph. Plotted millivolts on the abscissa.

Similarly, 25 ml of each groundwater sample was taken and analyzed in the same
manner and the potential measurements were recorded and estimated the corresponding
fluoride concentration from the standard curve (Clesceri et al., 1998; Greenjalgh and Riley,
1961).

3.3.2.2.7 Determination of PHOSPHATE ions UV/Vis spectrophotometrically at 880 nm

using acid antimony-phosphomolybdenum blue as complexing agent

This method is suitable for determining phosphate compounds in water in the form of
orthophosphate.

3.3.2.2.7.1 Solution preparation

• Sulfuric acid solution (5N): Diluted 70 ml conc. H2SO4 with a little deionized water in
500 ml beaker cooled and transferred to 500 ml volumetric flask and volume was made up
to mark with deionized water.

• Ascorbic acid solution (0.1M): Dissolved 1.76 g ascorbic acid in little deionized water
and volume was made up to 100 ml. This solution is stable for about 1 week at 4°C.

• Ammonium molybdate solution: Dissolved 20 g ammonium molybdate (NH4)6Mo7O24

4H2O in little deionized water and total volume was made up to 500 ml. Stored in a glass
stoppered bottle.

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 • Potassium antimony (III) oxide tartrate solution: Dissolved 1.3715 g of potassium
antimony (III) oxide tartrate (K(SbO) C4H4O6. 1/2 H2O) in little deionized water and volume
was made up to 500 ml. Stored in a glass stoppered bottle.

• Combined reagent mixture: Mixed the above reagents in the following proportions for
100 ml of the combined reagent. 50 ml 5N H2SO4, 5 ml potassium antimony oxy tartrate
solution, 15 ml ammonium molybdate solution and 30 ml ascorbic acid solution. Mixed after
the addition of each reagent in the order given. Left all the reagents to reach room
temperature before they were mixed. This solution remains stable for about 4 hours.

• Phosphate stock solution (1000 mg/L): Dissolved 1.432 g potassium dihydrogen

phosphate (KH2PO4) with little deionized water in 1000 ml volumetric flask and the total
volume was made. This solution remains stable for about one week.

• Phosphate working standard (10 mg/L): 1 ml of 1000 mg/L phosphate stock solution
was diluted to 100 ml with deionized water.

3.3.2.2.7.2 Procedure

Pipetted 40 ml each of the filtered samples into a 50 ml volumetric flask. Added

consecutively while shaking, 6.4 ml combined reagent solution and volume was made up to 50
ml with deionized water. Shaken well and left standing for about 10 to 30 minutes. Measured the
absorbance of each sample at 880 nm using reagent blank as reference solution. Phosphate
standard solutions 0.25, 0.5, 0.75, 1, 1.5, 2 mg/L respectively, were also prepared by diluting
appropriate volume of 10 mg/L phosphate working standard solution with little deionized water
into 50 ml volumetric flask, added 6.4 ml combined reagent solution and volume was made up
to 50 ml with deionized water and analyzed in the same way to obtain calibration curve (Clesceri
et al., 1998).

3.3.2.2.8 Determination of SULFATE ions gravimetrically

Sulfate is precipitated in a hydrochloric acid solution as barium sulfate by the addition of

barium chloride.

3.3.2.2.8.1 Solution preparation

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 • HCl solution (1+1): Carefully mixed 500 ml of conc. hydrochloric acid with 500 ml of
deionized water in 1000 ml beaker.

• Barium chloride solution (10%): Dissolved 100 g of barium chloride dihydrate (BaCl2.
2H2Or with deionized water in 1000 ml beaker. 1 ml of this solution is capable of
precipitating approximately 40 mg SO42- .

3.3.2.2.8.2 Procedure

To 50 ml of sample, 1-2 ml of HCl (1+1) solution was added in 100 ml beaker. Heated to
boiling on Bunsen burner, while stirring gently, slowly added barium chloride solution until
precipitation appeared to be completed, finally added about 2 ml in excess. Beaker was
covered with watch glass, cooled and placed preferably for over night but for not less than 2
hours. Filtered precipitate with Wattman 42 filter paper and washed residue with excess of
deionized water preferably 250 ml to remove chloride impurities. Placed filter paper and residue
in a weighed platinum crucible, charred first gently and not to let filter paper flamed then ignited
at high flame. Cooled in desiccator and weighed (Clesceri et al., 1998).

3.3.2.2.8.3 Calculation

Sulfate (SO42-) mg/L = wt of (BaSO4) precipitate x 0.4116 x 106 / vol. of sample taken

3.3.2.2.9 Determination of NITRATE ions by Ion Selective Electrode method

3.3.2.2.9.1 Solution preparation

• Nitrate stock solution (1000 mg/L NO3-N): Dissolved 6.0681 g of anhydrous sodium
nitrate (NaNO3) in little deionized water and volume was made to 1000 ml. Preserved the
solution with 2 ml Chloroform. This solution remains workable for 6 months.

• Nitrate working standard solutions: Prepared 1000, 100, and 10 ppm NO3-N
standard solutions by serial dilution of 1000 mg/L NO3-N standard solution in 100 ml
volumetric flasks with deionized water.

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• Ionic Strength Adjuster Buffer: To keep a constant background ionic strength,
prepared 2M ammonium sulfate ionic strength adjusting buffer by adding 26.4 g reagent
grade (NH4)2SO4 to a 100 ml volumetric flask, dissolved and diluted to the mark with
deionized water.

• Reference Electrode (Outer Chamber) filling solution: Added 2 ml ISA to 100 ml

deionized water. Used this solution to fill the outer chamber of the reference electrode.

3.3.2.2.9.2 Procedure

Ion meter (Orion, model 710A) was adjusted at millivolt mode. In order to construct
calibration graph, transferred 50 ml of 1000 mg/L NO3-N standard solution into 100 ml beaker
added 1-2 ml of ISA buffer solution and a magnetic bar. Immersed both, reference and NO3 ion
selective electrodes, while stirring on a magnetic stirrer measured developed potential. Let
electrodes were kept in the solution until reading was constant. Withdrawn electrodes rinsed
with deionized water and blot dried. Similarly 100 ad 10 ppm NO3-N standard solutions were
measured until constant reading at 56 ± 2 mV between each run. Plotted potential
measurements of NO3-N standards against concentration on two-cycle semi logarithmic graph
paper. Plotted milligrams NO3-N per liter on the logarithmic axis (ordinate), with the lowest
concentration at the bottom of the graph. Plotted millivolt readings on the abscissa.

Similarly, 50 ml of each groundwater sample was taken and analyzed in the same
manner and the potential measurements were recorded and finally estimated the corresponding
nitrate concentration from the standard curve (Clesceri et al., 1998)

3.3.2.2.9.3 Calculations

NO3 (mg/L) = Graph values of NO3 - N x 4.42

3.3.2.2.10 Determination of TOTAL DISSOLVED SOLID (TDS) Contents

Total dissolved solid (TDS) contents were determined in three ways for this study as
follows;

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3.3.2.2.10.1 By multiplying electrical conductivity values with an appropriate factor

This method provides general indication of the content of dissolved matter for water that
is not too saline or too dilute. The value of factor ranges from 0.55 to 0.7 for water containing
appreciable concentration of free acid or caustic alkalinity. This factor may be much lower than
0.55, and for highly saline water it may be much higher than 0.7. For most groundwaters the
value of the factor ranges between 0.6 and 0.7 (Logan, 1961). This method has been applied in
the field measurements of TDS by manually feeding a factor of 0.6 into Jenway combined
pH/Conductivity meter Model 430.

3.3.2.2.10.2 Evaporation to dryness method

Pipetted 50 ml of well mixed sample and transferred to a weighed evaporating dish and
evaporated to dryness on a steam bath. Dried for at least 1 hour in oven at 180 ± 2 °C, cooled in
a desiccator and weighed (Clesceri et al., 1998). TDS value can be calculated from the following
formula.

TDS (mg/L) = (A – B) x 106 / Sample volume

Whereas A= weight of dried residue + dish, B= weight of dish.

This method has been used for TDS estimation in the laboratory; however the results did
not agree with the theoretical values for TDS calculated from chemical analysis of sample.

3.3.2.2.10.3 To sum concentrations of various dissolved constituents

This method was finally adopted to report TDS values of groundwater samples collected
for this study. For certain type of water, these computed values may give a more useful
indication of total dissolved ions concentrations than the residue left by evaporation. (Clesceri et
al., 1998; Hem, 1989; Karath, 1989).

3.3.2.3 Trace Metals Analyses

3.3.2.3.1 Preparation of groundwater samples

Samples containing particulates or organic material generally require pretreatment

before spectroscopic analyses. To reduce these interferences and to convert metals to a form

93
that can be determined by atomic absorption spectrophotometry, nitric acid digestion method
was used because it digests most samples adequately.

Transferred 200 ml each of collected groundwater samples in a 300 ml beaker, added

10 ml of conc. HNO3 and heated at 70oC on hot plate. Brought to a slow boiling and evaporated
to the lowest volume possible (about 10-20 ml) before precipitation occurred. Continued heating
and added conc. HNO3 if necessary until digestion was completed as shown by a light colored
clear solution. Washed down beaker walls with deionized water and then filtered the sample.
Transferred filtrate to a 100 ml volumetric flask and volume was made up to the mark with
deionized water. Samples prepared in this way, were used for required metal determinations
(Clesceri et al., 1998; Chhatwal, 1997).

3.3.2.3.2 Determination of Trace Metals by Atomic Absorption Spectrophotometry

3.3.2.3.2.1 Solution preparation

Standard metal solutions (1000 ppm): Stock standard solutions (1000 mg/L) each of Cu,
Fe, Li, Mn, Sr, Zn, Al and Si were made available commercially (Merck).

• Working standards: Working standards of all stock standard solutions were prepared
appropriately by diluting the stock solutions of 1000 mg/L with deionized water for the
required range of unknown solution using standard addition technique.

3.3.2.3.2.2 Procedure

A series of standard solutions of each metal ion were simultaneously run in the
concentration range of unknown samples on Atomic Absorption Spectrophotometer. Calibration
curves of standard solution in the range of concentration of sample solutions were prepared.
Concentration versus absorbance was plotted for each metal. Calibration was made at four
points on standard solutions including blank. General analytical / measurement conditions have
been given in Table 3.2 for each metal ion determined. Concentration of unknown was read
directly from the instrument read out.

Hitachi model Z-5000 Atomic Absorption Spectrophotometer was used for analysis of
ground water samples collected from the study area. Hollow cathode lamps of respective metal
ions manufactured by Mitorika Company under the license of Hitachi Ltd. (Japan) were used
which provided narrow spectral lines of moderate intensity with Air-Acetylene system. This
instrument is capable of measuring metal ions within wavelength range of 190 - 900nm.

94