Rana et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(136-142)
International Journal of Research in Chemistry and Environment
Vol. 4 Issue 2 April 2014(136-142)
ISSN 2248-9649
Research Paper
Assessment of Physico-chemical Pollutants in Pharmaceutical Industrial
Wastewater of Pharma city, Selaqui, Dehradun
*Rana Rajender S.1, Prashant Singh1, Rakesh Singh2, Gupta Sanjay3
1
Department of Chemistry, DAV (PG) College, Dehradun, INDIA
Department of Chemistry, DBS (PG) College, Dehradun, INDIA
3
Department of Biotechnology & Biochemistry, SBSPGI, Balawala, Dehradun, INDIA
2
(Received 08th March 2014, Accepted 24th March 2014)
Available online at: www.ijrce.org
Abstract: Water pollution is a great challenge of today’s civilization. In Dehradun district of
Uttarakhand state during past 10 years, there is an extreme growth registered in pharmaceutical
industry. This rapid industrialization contributes to water pollution in and around Dehradun district.
Although, these pharmaceutical industries work under the strict guideline of Central Pollution Control
Board (CPCB), Govt. of India, but the situation is far from satisfaction. Time to time monitoring of
pharmaceutical wastewater is necessary to check the level of pollutants, which helps in upgradation and
designing of proper treatment strategy. In this study, we selected five different sites, located in Pharma
City, Selaqui, Dehradun, Uttrakhand, India, for wastewater assessment. pH, total suspended solids
(TSS), total dissolved solids (TDS), electrical conductivity (EC), chloride, phenols, chemical oxygen
demand (COD), biochemical oxygen demand (BOD), boron, sulphate, nitrate, fluoride and sodium
absorption ratio (SAR) were selected for wastewater assessment. Twelve months sampling (January 2012
to December 2012) was carried out and analysis was done every month for physico-chemical study. All
parameters were compared with the general standards for discharge of industrial effluents into inland
surface water, provided by CPCB and Bureau of Indian standards (BIS). The range of concentrations of
all parameters for five different sampling sites were found in the following range 4.66-6.95 for pH, 87408 mg/L for TSS, 764-4456 mg/L for TDS, 1168-6778 (µS/cm)for EC, 45-732 mg/L for chloride, 0-4.62
mg/L for phenolic compounds, 823-3302 mg/L for COD, 102-390 mg/L for BOD, 0-1.45 mg/L for boron,
37-837 mg/L for sulphate, 0.12-16.8 mg/L for nitrate, 0-0.89 mg/L for fluoride and 3.78-21.23 for SAR.
Further this study was subjected to statistical analysis by using Box and Whisker Vertical Plots,
Pearson’s Correlation and Annova. It was concluded that in all sampling sites, average value for
phenolic compounds, COD and BOD parameters were found above the standards limits and for pH,
chloride, boron, sulphate, nitrate and fluoride it was found below the standard limits provided by CPCB
and BIS. This study further helps us to design an appropriate treatment plan for pharmaceutical
industries wastewater containing other pollutants.
Keywords: Assessment, Pharmaceutical industries, Selaqui, Wastewater.
Introduction
enhanced the level of surface water pollution up to 20
times the safe level in 22 critical polluted areas of the
country. It is found that almost all rivers are polluted
in most of the stretches by some industries[4,5]. Level
of wastewater pollution varies from industry to
industry depending upon the type of processes and the
size of the industries[6].
The worldwide growth and expeditious
industrialization have led to the recognition and
increasing understanding of the interrelationship
between pollution, public health and environment.
Presently, 3.4 million people die each year in the
world from water borne diseases owing to rapid
industrialization[1,2]. The surface water is the main
source of industries for wastewater disposal[3].
Untreated or allegedly treated industrial effluents have
In India, during the past few decades
pharmaceutical industries have registered a quantum
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Rana et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(136-142)
jump. Pharmaceutical industry production includes
raw material, antibiotics, variety of medicines and
cosmetic products, which in turn generates the effluent
containing constituents harmful to human and aquatic
life[7,8]. Although, maintenance and housekeeping
activities are similar from one plant to another, but
pharmaceutical industries do not generate uniform
waste streams, due to the variety of medicines
produced during any given manufacturing process[8,912]
. Though the volume of untreated or incompletely
treated pharmaceutical industrial wastewater (PIWW)
is small but it contains high level of pollutants because
of the presence of non-biodegradable organic matter,
heavy metals (such as Lead, Mercury, Cadmium,
Nickel, Chromium) and other pollutants[13-15].
Predicted impacts of the wastewater on the flora and
fauna vary widely due to the wide variations in the
characteristics of the wastewater. When these
pollutants are discharged on the ground or in the water
bodies, they accumulate in the system through the food
chain and affect the human health and other living
organisms[16].
monitoring further helps in wastewater treatment plan.
Previous study on PIWW reveals the presence of
organic and inorganic pollutants[4,9,13,17-18]. The
proportionate increased level of water pollution in and
around Dehradun[19], generates a need for assessment
of physico-chemical contaminants in PIWW of
Pharmacity, Selaqui, Dehradun, Uttarakhand, India.
Material and Methods
Sampling area and sample preparation: Water
pollution level of nearby area of Selaqui region of
Dehradun district is increasing[19] due to improper
treatment of wastewater discharged from industrial
area of Selaqui, Dehradun, Uttrakhand, India.
Therefore, the Pharmaceutical Industrial Area (Pharma
City), Selaqui was chosen for the study, which is
located 25 km from Dehradun, the capital of
Uttrakhand State. Samples were collected from five
different sampling sites, designated as S1 to S5.
Wastewater samples were collected from the discharge
point near RFCL Bridge designated as S1, near Round
Chowk as S2, near TVS Electronics as S3, near IGL as
S4 and S5 was located at near Netco Pharma.
Wastewater samples were collected in 1 litre Tarson
sampling bottles previously cleaned by washing with
non-ionic detergent, rinsed with tap water and later
soaked in 10% HNO3 for 24 hours and finally rinsed
with deionised water prior to use.
Assessment of PIWW is necessary to evaluate
the pollutants level and also for its reuse in different
other process. Agriculture is the major user of water
that can accept lower quality water than domestic and
industrial users. It is, therefore, unavoidable that there
will be a growing tendency to look toward irrigated
agriculture for solutions to the overall effluent disposal
problem. Although all pharmaceutical industries work
under the strict guideline of CPCB but untreated or
improperly treated wastewater generation requires a
time to time monitoring of wastewater. CPCB and BIS
provide general standards for discharge of industrial
effluents into inland surface water.
During sampling, sample bottles were rinsed
with sample water three times and then wastewater
was filled from each of the five designated sampling
points (S1 to S5). The samples were labelled and
transported to the State Level Water Quality Analysis
Laboratory, Uttarakhand Jal Sansthan, Dehradun and
stored at 60C in refrigerator.
Table 1
Water Quality Standards for water use in
irrigation and industrial cooling
(Source IS 2296:1992)
Characteristics (all
parameters in mg/l, max
except pH, EC, SAR)
pH
TDS
Chlorides
Sulphates
EC, (µS/cm) max
Sodium absorption ratio
(SAR), max
Boron
All parameters were analysed as per standard
method[20]. Assessment of pH, TDS and EC were done
on site itself. For pH assessment, Chlorine/pH Meter
(Pocket ColorimeterTMII; Make: HACH, USA) and for
TDS & EC analysis, TDS/Conductivity meter (HACHsension5) were used. Sulphate, nitrate and fluoride
were analysed by spectrophotometer (Model: DR
5000; Make: HACH, USA).
For Irrigation and
Industrial Cooling
(Class E)
6.0-8.5
For SAR estimation, assessment of sodium,
calcium and magnesium were done by atomic
absorption spectrophotometer (Model: AA 240A;
Make: Varian, Australia). SAR was calculated by
following formula:
2,100
600
1,000
2,250
26
SAR = Na / [ (Ca+Mg) / 2]0.5
Statistical analysis: The data obtained were subjected
to statistical analysis using “Graph Pad Prism 5”
software. By using this software box and whisker
plots, analysis of variance (ANOVA) and Pearson’s
correlation were observed. With the help of box and
2
Previous data on water pollution caused by
pharmaceutical industries points out the need of
regular monitoring of pollution level and this
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Rana et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(136-142)
whisker plots, estimation of the range (minimum to
maximum), median, mean, interquartile range were
done. Box plots can be drawn either horizontally or
vertically[21,22].
Results and Discussion
Box and whisker plots are shown in Figure 1
to 13, shows the minimum to maximum limits and
mean value (+) of parameters for each sampling sites.
Figure 4: Box and Whisker Plot of EC analysed at
5 sites of Pharmacity, Dehradun
Figure 1: Box and Whisker Plot of pH analysed at 5
sites of Pharmacity, Dehradun
Figure 5: Box and Whisker Plot of Chloride
analysed at 5 sites of Pharmacity, Dehradun
Figure 2: Box and Whisker Plot of TSS analysed at
5 sites of Pharmacity, Dehradun
Figure 6: Box and Whisker Plot of Phenols
analysed at 5 sites of Pharmacity, Dehradun
Figure 7: Box and Whisker Plot of COD analysed
at 5 sites of Pharmacity, Dehradun
Figure 3: Box and Whisker Plot of TDS analysed at
5 sites of Pharmacity, Dehradun
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Rana et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(136-142)
Figure 8: Box and Whisker Plot of BOD analysed
at 5 sites of Pharmacity, Dehradun
Figure 11: Box and Whisker Plot of Nitrate
analysed at 5 sites of Pharmacity, Dehradun
Figure 9: Box and Whisker Plot of Boron analysed
at 5 sites of Pharmacity, Dehradun
Figure 12: Box and Whisker Plot of Fluoride
analysed at 5 sites of Pharmacity, Dehradun
Figure 10: Box and Whisker Plot of Sulphate
analysed at 5 sites of Pharmacity, Dehradun
Figure 13: Box and Whisker Plot of SAR analysed
at 5 sites of Pharmacity, Dehradun
From these plots it was observed that the
maximum value of pH found in S2 sampling sites
(6.95) and minimum in S2 (4.66), maximum
concentration of phenols found in S5 (4.62 mg/l) and
minimum in S3 (0 mg/L), maximum concentration of
COD found in S5 (3302 mg/l) and minimum in S3
(823 mg/L), maximum concentration of BOD found
in S5 (390 mg/l) and minimum in S1 (102 mg/L),
maximum concentration of boron found in S5 (1.45
mg/l) and minimum in S2 and S3 (0 mg/L),
maximum concentration of sulphate found in S5 (837
mg/l) and minimum in S4 (37 mg/L), maximum
concentration of nitrate found in S3 (16.8 mg/l) and
minimum in S4 (0.12 mg/L), maximum
concentration of fluoride found in S3 (0.89 mg/l) and
minimum in S1 and S4 (0 mg/L), maximum
concentration of chloride found in S2 (732 mg/l) and
minimum in S1 (45 mg/L), maximum concentration
of TSS found in S4 (408 mg/l) and minimum in S1
(87 mg/L), maximum concentration of TDS found in
S5 (4456 mg/l) and minimum in S1 (764 mg/L),
maximum value of EC found in S5 (6778 µS/cm) and
minimum in S1 (1165 µS/cm), maximum value of
SAR found in S5 (21.23 and minimum in S3 3.78).
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Rana et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(136-142)
From Table 2, it was observed that average
values of pH, chloride, boron, sulphate, nitrate and
fluoride, in all sampling sites were found under the
tolerance limit provided by Indian standard (standard
A and B). In all sampling sites, the average values of
TSS, COD, BOD and phenols were found above the
standard tolerance limit.
between the following parameters: EC-TDS (0.999),
SAR-TDS (0.776), SAR-EC (0.775), SAR-Sulphate
(0.719), Sulphate-Chloride (0.676), Sulphate-TDS
(0.655), Sulphate-EC (0.651), Chloride-TDS (0.645),
Chloride-EC (0.638), SAR-BOD (0.578), SARChloride (0.565), COD-TDS (0.537), SAR-COD
(0.518), Phenols-TDS (0.516), Phenols-EC (0.514)
and COD-EC (0.514). And high negative correlation
exhibit between the following parameters: NitrateTDS (-0.331), Nitrate-EC (-0.327), Nitrate-Chloride
(-0.291), Nitrate-Sulphate (-0.291), SAR-Nitrate (0.261), Fluoride- Phenols (-0.254) and Fluoride-pH
(-0.240). The result of ANOVA (one way) for all
parameters has shown in Table 4. From the above
table it was concluded that there is a significant
difference observed for all parameters except pH.
Pearson’s correlation coefficient matrix:
Earlier researcher reported the correlation between
water quality parameters, which showed strong
positive and strong negative correlation[23,24]. In this
study Pearson’s correlation coefficient matrix was
prepared between the analysed parameters and shown
in Table 3. From this table, it is observe that high
positive correlations among all the parameters exhibit
Table 2
Comparison of average value of parameters with tolerance limits for discharge of industrial effluents into
inland surface, provided by CPCB and BIS (IS: 2490, Part-I-1981)
S. No.
Parameters
Sampling Sites
Standard A
(CPCB)
S1
S2
S3
S4
S5
5.89
151
1588
2452
5.75
159
2304
3505
5.71
186
1830
2798
5.79
215
1836
2804
5.76
184
2735
4183
5.5-9.0
100
-
Standard B
(IS:2490,
part-1-1981)
5.5-9.0
100
-
1
2
3
4
pH
TSS (mg/L)
TDS (mg/L)
EC (µS/cm)
5
6
7
8
9
Chloride (mg/L)
Phenols (mg/L)
COD (mg/L)
BOD (mg/L)
Boron (mg/L)
142
1.685
1564
182.3
0.2798
375
2.013
1879
227.9
0.2384
229
1.279
1692
194.08
0.2279
231
2.042
1594
204.4
0.1912
420
2.342
2159
255.1
0.5612
1
250
30
-
1000
1
250
30
2
10
Sulphate (mg/L)
166
362
216
138
374
-
1000
11
Nitrate (mg/L)
8.25
4.295
8.19
1.7
2.48
10
-
12
Fluoride (mg/L)
0.222
0.625
0.559
0.202
0.418
2
2
13
SAR
5.42
8.02
5.85
6.0
9.17
-
-
pH
TDS
EC
Chloride
Phenols
COD
BOD
Boron
Sulphate
Nitrate
Fluoride
SAR
pH
1.000
-0.111
-0.115
-0.037
0.131
0.058
0.070
0.250
-0.041
0.005
-0.240
-0.046
TDS
EC
1.000
0.999
0.645
0.516
0.537
0.573
0.197
0.655
-0.331
0.127
0.776
1.000
0.638
0.514
0.537
0.566
0.194
0.651
-0.327
0.122
0.775
Table 3
Correlation between all parameters
Chloride Phenols COD BOD Boron Sulphate Nitrate Fluoride SAR
1.000
0.431
0.410
0.368
0.248
0.676
-0.291
0.247
0.565
1.000
0.401
0.416
0.332
0.421
-0.173
-0.254
0.435
1.000
0.670
0.216
0.461
-0.027
0.011
0.518
[140]
1.000
0.160
0.456
-0.169
-0.0385
0.578
1.000
0.141
-0.133
-0.120
0.141
1.000
-0.291
0.109
0.719
1.000
0.022 1.000
-0.261 -0.007
1.000
Rana et al. Int. J. Res. Chem. Environ. Vol.4 Issue 2 April 2014(136-142)
Table 4
Result of analysis of variance for all parameters
pH
P value
TDS
EC Chloride Phenols COD BOD Boron Sulphate Nitrate Fluoride SAR
<
<
0.0004 0.0004 0.026 0.027 0.0121 0.003
0.0001 0.0001
ns
***
***
***
***
*
*
*
**
0.978
P value summary
Are means
significant
different? (P< 0.05)
Number of groups
No
Yes
Yes
Yes
Yes
5
5
5
5
5
Yes Yes
5
5
<
< 0.0001 0.001
0.0001
***
***
***
Yes
Yes
Yes
Yes
Yes
5
5
5
5
5
5.39
F
0.110 7.568 7.499
6.132
6.132 2.990 2.967 3.544
4.50
8.912
9.867
R squared
0.008 0.355 0.352
0.308
0.308 0.178 0.177 0.204
0.246
0.393
0.417 0.281
Conclusion
Sansthan (UJS,) Dehradun is also duly acknowledged
for technical support.
This study enable us to conclude that average
value of pH, chloride, boron, sulphate, nitrate and
fluoride were found within the tolerance limits for
discharge of wastewater into inland surface,
recommended by CPCB and BIS. The average
concentration of TSS, phenols, COD and BOD were
found above the tolerance limit provided by CPCB and
BIS for discharge of wastewater into inland surface or
water streams. Wastewater treatment is necessary for
reuse of water for agriculture purpose because
agriculture is a major site which can accept lower
grade of water. From the Table 1, provided by BIS,
indicated that some selected parameter such as
sulphate, chloride, SAR and boron were found within
the permissible limit and there is a no need for
treatment of these parameters in PIWW.
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