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DOI 10.1007/s10661-009-0815-y
Received: 7 August 2008 / Accepted: 27 January 2009 / Published online: 27 March 2009
© Springer Science + Business Media B.V. 2009
Department of Environment, Forests & Wildlife, Gulf of Katchchh (Fig. 1). This port has many ter-
Government of India, New Delhi were followed to minals for handling oil and oil products, fertilizers,
assess the pollution levels in marine waters. In the and general cargo. Hectic loading and unloading
present communication, the large data matrix ob- activities and movement of personnel at the port
tained during the monitoring program (1,224 ob- are bound to have adverse effects on the creek
servations) in Kandla creek was utilized to extract water. Tidal height in the creek ranges from 0.83
information on: (a) the temporal variations and to 7.2 m and a surface current varies from 1.5 to
(b) evaluate the significant sources contributing to 5 kn.
water quality parameters.
Sampling and analysis
5'
23˚
00'
55'
Environ Monit Assess (2010) 163:49–56 51
Fig. 2 Temporal
variations—box plot
for selected parameters
for three seasons (S1
premonsoon, S2
monsoon, S3 post
monsoon)
52 Environ Monit Assess (2010) 163:49–56
creeks meet Kandla creek (Fig. 1), over a 2-year tends to minimize the influence of variance of
period from October 2002 to September 2003 and parameters. It also eliminates the influence of
June 2004 to May 2005. The water samples were different units of measurement and renders the
collected from surface, mid-depth, and bottom data dimensionless. The main concern of the
water layers at each station and on-the-spot PCA is to understand the mode of action or
analyses were made for few parameters while for behavior of components of a system and its
other parameters, the samples were analyzed at subsystems (Petersen et al. 2001; Bengraine
the shore laboratory following standard methods and Marhaba 2003). The use of PCA for wa-
for water analysis (APHA 1975; Grasshoff et al. ter quality assessment has increased in the
1983). Water quality variables analyzed include last few years, mainly due to the need to
dissolved oxygen (DO), water temperature obtain appreciable data reduction for analysis
(TEMP), pH, salinity (SAL), suspended solids and decision (Morales et al. 1999). Bartlett’s
(SSOL), biochemical oxygen demand (BOD), sphericity test (χ 2 with degrees of freedom =
phosphate (PO4 –P), nitrite (NO2 –N), nitrate 1/2[ p( p − 1)]) was used to verify the applicability
(NO3 –N), ammonia (NH3 –N), and silicate (Si2 of PCA to raw data (Stevens 1986). The STATIS-
O3 –Si). Turbidity (TURB) was measured by TICA 6.0 software package was employed for data
nephelometric method. Dissolved/dispersed pe- treatment.
troleum hydrocarbons (PHC) were extracted
from seawater with double distilled hexane and
quantified by using Shimadzu RF-1501 fluores- Results and discussion
cence spectrofluorometer. Phenol (PHE) was ex-
tracted with chloroform after complexing with Exploratory data analysis
4-aminoantipyrene, and the color was measured
spectrophotometrically. For estimation of chlo- Box plots of selected parameters during three
rophyll a (CHL), 500 ml of water sample was seasons (Fig. 2) at four sampling stations were
filtered through GF/F glass fiber filter paper examined. By inspecting these plots, it was possi-
extracted in 90% acetone overnight. The extracts ble to perceive differences between the seasons.
were used for the estimation of fluorescence be- Our first approach to establish the parameter-
fore and after acidification using Turner Design associated temporal variation was by use of the
Fluorometer. The fluorescence values were con- Spearman R. The bivariate results (Table 1) show
verted to chlorophyll and phaeophytin (PHAE) that the five parameters having significant cor-
using appropriate calibration factor. Primary relation with the season ( p < 0.05) are: nitrates,
production (PP) was measured using 14 C tech- suspended solids, ammonia, water temperature,
nique. The data quality was checked by careful
standardization and procedural blank measure-
ments of spiked and duplicate samples. Table 1 Spearman non-parametric correlation coefficient
(R) for selected parameters between seasons (bold figures
Multivariate statistical methods indicate significance at p < 0.05)
Parameters Summer and Summer and Monsoon
The water quality parameters in three different monsoon winter and winter
seasons (winter, summer, and monsoon) were as- TEMP −0.39 − 0.78 0.34
signed a numerical value in the data file which, DO −0.22 0.28 0.08
BOD 0.06 0.30 0.05
as a variable corresponding to the season, was
TURB 0.71 0.38 0.37
correlated (pair by pair) with all the measured SSOL 0.93 0.62 0.64
parameters. CHL −0.21 0.74 −0.35
In order to avoid misclassification due to wide NO3 0.48 0.84 0.55
differences in data dimensionality (Ross 1988), NH3 0.50 0.38 0.86
data was standardized through z-scale transfor- PHC 0.24 0.12 0.31
mation before applying PCA. Standardization PHE 0.27 0.25 0.22
Environ Monit Assess (2010) 163:49–56 53
and turbidity. The season-correlated parameters indicate the percent contribution of correspond-
were taken as representing the major source of ing variable to the PC and are called the loading
temporal variations in water quality. In view of of ith variable in kth PC (correlation between
the source types in the creek, these correlations variable ith and kth PC). These loading values
can be explained on the basis of seasonal features were used to group variables in PCs.
in the monitoring region. The correlation matrix Score value (skj) for jth observation in kth PC
suggests that the temperature, SSOL, NO3 , and was obtained from the weight of variables in PCs
NH3 are the most significant parameters to dis- and standardized variables by using the following
criminate between the seasons, which also means equation:
that these parameters account for most of the
expected temporal variations in the water qual- skj = a1 j z1 j + a2k z2 j + − − − − − − − + a pk z pj
ity; this also suggests that the anthropogenic in-
put, which was the major pollution source mainly where j = 1, 2, . . ., n is the number of obser-
derived from the discharge of wastewater into vations; k = 1, 2, . . ., q the number of selected
the system, was independent of the season as it PC numbers, and p the number of independent
was present throughout the year. Some of these variables.
correlations can be explained by climatic changes By applying Bartlett’s sphericity test, a value
associated with the three seasons. Land drainage of 844.764 for the Bartlett chi-square statistics
and strong tidal currents in the creek bring in a was found (df = 136, p < 0.01), confirming that
large amount of colloidal particles into suspen- the parameters are not orthogonal but correlated,
sion during monsoon, whereas, during summer, therefore explaining the data variability with
the strong tidal currents in low water level of a lesser number of parameters (called principal
the creek disturb the settled sediments bringing components).
in large amount of colloidal particles in water, PCA on 17 parameters yielded five principal
thereby increasing the turbidity. This was also components explaining sample variance of about
true for suspended solids, which were significantly 76% (Table 2). The varimax rotation was then
higher during the summer and winter periods as performed to secure increased principal compo-
compared to the monsoon. Although instances of nents of environmental significance; a similar ap-
waste releases due to port activities were evident proach based on PCA has been used to identify
in Kandla creek, the influence of seasonal changes the main components in water quality (Vega et al.
appears to be fairly large. 1998; Helena et al. 2000; Wunderlin et al. 2001;
Simeonov et al. 2003; Singh et al. 2004).
Data treatment In the present study, the first PC that explains
29% of total variance has significant loadings
In the application of PCA to water quality data (> 0.70) on salinity, suspended solids, turbidity,
from Kandla Port monitoring stations, correlation and petroleum hydrocarbons (Fig. 3). High load-
matrix of variables (R p× p ) was used to obtain ings on suspended solids, turbidity, and salinity
eigenvalues and weights of parameters. Since the were due to the natural effects of strong tidal
four sampling stations were combined to calculate currents (tidal range 7 m) and intrusion of saline
the correlation matrix, the correlation coefficients
should be interpreted with caution as they are
simultaneously affected both by spatial and tem- Table 2 Eigenvalues and percentage of explained variance
poral variations. The Scree plot was used here to by first five components by PCA
identify the number of PCs to be retained in or- Component Eigenvalue % total variance Cumulative %
der to comprehend the underlying data structure 1 4.922 28.95 28.95
(Jackson 1993). Eigenvector λ was used to obtain 2 4.282 25.18 54.13
unrotated factor loadings. Via indicates the values 3 1.588 9.34 63.47
of rotated factor loadings, which were obtained 4 1.107 6.51 69.98
by varimax rotation. Rotated loadings in PCs 5 1.018 5.99 75.97
54 Environ Monit Assess (2010) 163:49–56
Factor 1
1
Factor loadings
0.8
0.6
0.4
0.2
0
0.2
0.4
0.6
Factor 2
1
Factor loadings
0.8
0.6
0.4
0.2
0
0.2
0.4
0.6
0.8
1 Factor 3
0.8
Factor loadings
0.6
0.4
0.2
0
0.2
0.4
0.6
1 Factor 4
0.8
Factor loadings
0.6
0.4
0.2
0
0.2
0.4
0.6
0.8
1
1 Factor 5
0.8
0.6
Factor loadings
0.4
0.2
0
0.2
0.4
0.6
0.8
1
-1.2
TEMP PH SAL DO BOD SSOL TURB PO4 NO2 NO3 NH3 SILI PHC PHE PHAE CHL PP
waters from the salt works. The high loading of from fields after precipitation events. Within the
petroleum hydrocarbons was due to the spillage part of variance described by the third PC, tem-
from loading and unloading activities of oil and perature and pH have an opposite sign in com-
other petroleum products. The second PC that parison to the DO and BOD. The contribution
explains 25% of the total variance correlates to of salinity was negligible; phosphate and nutrients
water-soluble nitrogenous species, i.e., NO2 –N, were only weakly involved (Fig. 3). The pattern
NO3 –N, NH3 –N, and petroleum hydrocarbons can be interpreted in terms of biological activity
(Fig. 3). The main sources of nitrate were due to as either primary production by algae or their
agricultural activities and the increased drainage subsequent microbial decomposition. The fourth
Environ Monit Assess (2010) 163:49–56 55
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