A Baseline Study of Physico-Chemical Parameters and Trace Metals in Waters of Ennore Creek, Chennai, India
A Baseline Study of Physico-Chemical Parameters and Trace Metals in Waters of Ennore Creek, Chennai, India
A Baseline Study of Physico-Chemical Parameters and Trace Metals in Waters of Ennore Creek, Chennai, India
www.elsevier.com/locate/marpolbul
Baseline
The objective of BASELINE is to publish short communications on different aspects of pollution of the marine
environment. Only those papers which clearly identify the quality of the data will be considered for publication.
Contributors to Baseline should refer to ‘Baseline—The New Format and Content’ (Mar. Pollut. Bull. 42, 703–704).
a
Department of Applied Geology, School of Earth & Atmospheric Sciences, University of Madras, Guindy Campus, Chennai 600 025, India
b
Department of Geology, Anna University, Chennai 600 025, India
c
Department of Geology, School of Earth & Atmospheric Sciences, University of Madras, Guindy Campus, Chennai 600 025, India
Chennai (Madras) is a metropolitan city with a high- eco-system surrounding Ennore Creek has been severely
density population of 4 million (as well as 1.5 million distorted. This study presents baseline data for Ennore
floating population) and is drained by the Adyar River Creek, and the impacts due to the development of major
in the south, Cooum River in the central part and En- industries in Chennai.
nore Creek on the northern side. Ennore Creek is a Surface water samples (40) were collected (20 samples
fresh/brackish water system, which is nearly 800 m wide in each season) using a non-metallic aqua-trap water
and elongated in a NE–SW direction. Ennore Creek is sampler during two monitoring programs in monsoon
complex, the average depth rarely exceeding 5 m in the and non-monsoon seasons during 2000 and 2001 (Fig.
non-monsoon period, being fed by Kortalaiyar River, 1). Temperature was determined using a reversible ther-
and the Buckingham Canal; it is also connected to the mometer and pH was measured on board immediately
Pulicat brackish water lake on the northern side, which after collection. The water samples were collected in
once nurtured rich fauna and flora, including man- polypropylene plastic bottles, which were pre-cleaned
groves. However, in recent years, the discharge of efflu- with 1 N HCl and the samples were kept in an icebox
ents from major industries including fertilizers, rubber onboard immediately after collection. Analyses of dis-
factories, steel rolling, motor vehicles, oil refineries and solved nitrite (NO2 ), nitrate (NO3 ), phosphate
operations of the second major harbour for coal import, (PO4 3 ) and silicate [SiðOHÞ4 ] were determined using
which includes a thermal power plant situated nearby, spectrophotometer procedures described by Parsons
has imparted severe stress on the estuarine ecosystem. et al. (1984). Na+ and K+ concentrations were deter-
Due to mounting population and the development of mined with a flame photometer using suitable chemical
major industries during the past three decades, the standards. Ca2+ and Mg2+ were determined based on
the methods of Culkin and Cox (1966) by titrating the
*
water samples to photometric end points with EGTA
Corresponding author. Present address: Centro de Investigaciones using Zincon Zn-EGTA indicator. Trace element studies
en Ciencias de la Tierra, Universidad Autónoma del Estado de
Hidalgo, Ciudad Universitaria, Carretera Pachuca-Tulancingo Km.
were performed on samples preserved with 2 ml of conc.
4.5, Pachuca, Hidalgo, C.Postal. 42184, Mexico. HNO3 (1 l). Concentrations of Fe, Mn, Cr, Cu, Ni, Co,
E-mail address: [email protected] (M.P. Jonathan). Pb, Zn and Cd were determined in unfiltered samples
584 Baseline / Marine Pollution Bulletin 50 (2005) 583–608
(a) (k)
40 360
Ca2+ (mg/L)
Temp˚C
35 300
30 240
25 180
Mg2+ (mg/L)
700
pH 8
600
7 500
Fe (µg/L)
4 4000
2 2000
0 0
37 (d) 45 (n)
32
Mn (µg/L)
Sal (‰)
30
27
15
22
17 0
Cr (µg/L)
3
0.5
2
1
0.0 0
90 (f) 8 (p)
NO3- (µg.L-1)
6
Cu (µg/L)
60
4
30
2
0 0
Si(OH)4- (µg.L-1)
60 (g) 12 (q)
9
Ni (µg/L)
40
6
20
3
0 0
20 (h) 8 (r)
PO43- (µg.L-1)
15 6
Co (µg/L)
10 4
5 2
0 0
18 (i) 30 (s)
Na+ (mg/L)
Pb (µg/L)
16 20
14 10
12 0
450 80 (t)
(j)
60
K+ (mg/L)
Zn (µg/L)
400
350 40
300 20
250 0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Stations 0.5 (u)
0.4
Cd (µg/L)
0.3
× Year 2000 ◊ Year 2002 0.2
TNPCB Values (TNPCB, 2000) 0.1
0.0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Stations
Fig. 2. Distribution of nutrients and trace metals in surface waters of Ennore Creek, Chennai.
23.4 to 28.5 lg l1 in 2000 and 22.3 to 34.5 lg l1 in at the western end of Ennore Creek could be due to re-
2001 (Fig. 2g). The distribution pattern indicates high moval of silica by biological processes. In addition, the
concentration at the creek mouth with a gradual down- low levels at these stations could be due to dilution ef-
stream decrease, in conformity with the patterns found fects with considerable run off, thus limiting the build-
in most estuaries. The low level of silicate concentration up of free silica in the water column. SiðOHÞ4 could
586 Baseline / Marine Pollution Bulletin 50 (2005) 583–608
also decrease with increases in salinity due to geological and the domination of nitrate in F2 of both seasons
reactions involving clay minerals or due to properties of indicate the influence of industrial effluents where in-
two different masses (Boyle et al., 1974). During both creased form of nitrite and nitrate occurs due to death
seasons, PO4 3 values indicate increased values at low and decay of plankton. In addition, it could be due to
salinity zones (stations 1–4) and the inverse negative val- irrigation bacteria, and increased bacterial activity,
ues of PO4 3 vs. salinity (r = 0.74, 0.24) indicate that which is expected in the silty-clayey substratum, com-
simple dilution has taken place in high salinity zone areas pared to the low values in the sandy substrate near the
(Balls, 1992) (Fig. 2h). It is evident in Ennore Creek that mouth. The relationship between salinity vs. nitrite
the low river inflow in summer and the high temperature (r = 0.71, 0.69), nitrate (r = 0.73, 0.51) and silicate
of water in mid-creek result in mineralization associated (r = 0.31, 0.53) was positive, whereas, phosphate showed
with the more turbid layer of water. This is clearly attrib- reverse concentration against other nutrients in compar-
uted by the low level of DO with high temperatures ison; this is also well supported by the high negative
and increase in nitrate concentrations downstream, as values in factor analysis of both seasons. Comparatively
oxygen is consumed. Irregular pockets of high PO4 3 at higher values of phosphate were obtained where the
stations 6–8, 13–15 during 2000 exhibits behaviour of a influence of fresh effluents was more. Therefore, the
transition period when any phosphate build-up is inhib- source of phosphate for this creek may be external.
ited by algal growth (Lakshmanan et al., 1987). Desorption of phosphate is favoured by an alkaline
Correlation matrix analysis of the physico-chemical environment (pH > 8) indicating anthropogenic activi-
parameters indicated mixed correlation between temper- ties (Flegal et al., 1991; Clark et al., 1992). The study
ature and pH indicating a separate behaviour for both also revealed that the concentrations of nitrates and
these parameters. Among the four nutrients studied, phosphate have increased appreciably over the years
phosphate showed more pronounced spatial variability and the complete off set of low tidal activity due to the
than nitrite, nitrate and silicate. The positive correlation closed nature of the mouth during non-monsoon peri-
of DO vs. salinity (r = 0.64, 0.73), nitrite (r = 0.59, 0.33), ods. This is attributable to the discharge from fertilizer
nitrate (r = 0.61, 0.49), silicate (r = 0.38, 0.54) during factory wastes, alkaline chemicals and untreated domes-
both years and the domination in F1 indicate that the tic sewage containing these substances and their persis-
water entering the creek is practically in an under satu- tence due to inadequate flushing (Ganapathi and
rated condition and that saturation of creek water is not Raman, 1979; Raman, 1995).
possible in the mixing zone of the creek (Ghosh et al., Sodium and potassium concentrations reveal similar-
1991). The positive NO2 vs. NO3 (r = 0.96, 0.68) ity with salinity concentration (Fig. 2i and j). High val-
Baseline / Marine Pollution Bulletin 50 (2005) 583–608 587
ues of Na+ and K+ are seen at the mouth of the creek dissolved Mn adsorption could be on suspended particu-
indicating the dominance of low level seawater intrusion late matter and, in higher saline regions, could be derived
at various periods, similar to other estuarine conditions from desorption from suspended particulate matter
in south Indian rivers (Ramanathan et al., 1988). The (Knox et al., 1981; Manjunatha and Shankar, 2000).
increase in potassium concentration of >300 mg/l indi- Fe and Mn have been studied in a number of estuarine
cates considerable influence of river water as it traverses and coastal regions (Callaway et al., 1988; Paulson
through Gondwana clay formations in the northern et al., 1989) but in the present study both Fe and Mn
Chennai region, which contains considerable amounts show a similar trend during both the years. Both the
of potassium in the form of illite as the dominant clay elements (Fe, Mn) indicate removal via colloidal floccu-
mineral (Selvaraj, 1999). The positive correlation of lation on the down streamside and show very high
Na+ vs. salinity (r = 0.94, 0.84) and K+ vs. salinity concentrations (stations 1–6). The correlation of Fe vs.
(r = 0.53, 0.67) indicates that they are strongly inter- PO4 3 (r = 0.76, 0.21) and Mn vs. PO4 3 (r = 0.80,
related. The concentrations of major cations Ca2+ and 0.29) indicates that colloidal flocculation has also re-
Mg2+ are similar to salinity values with higher values moved the phosphate (Church, 1986). The results also
at stations 18–20 (Fig. 2k and l). The correlation of indicate that as pH increases with salinity, Fe and Mn
Ca (r = 0.81, 0.73) and Mg (r = 0.30, 0.74) with salinity start precipitating on the downstream side rather than
in both the years indicates that addition of Ca2+ and at the mouth of the Ennore Creek (Byrd et al., 1990).
Mg2+ is taking place in the mouth of the Ennore Creek Analysis of toxic trace elements Cr, Cu, Ni, Co, Pb,
and examination of the data revealed almost a constant Zn and Cd indicates considerable fluctuations (Fig.
increase of both the cations against salinity gradient. 2o–u). A general trend of enrichment with respect to in-
The addition of Ca2+ and Mg2+ in higher salinity region crease in salinity and temperature is seen in all the met-
indicates that no removal has taken place; instead it has als. On average, the high concentrations found in lower
precipitated at the mouth of the creek as the ionic salinity zones in the study are all above the Tamil Nadu
strength has increased. Ca2+ (269–354 mg/l) and Mg2+ Government Pollution Control Board values (TNPCB,
(683–805 mg/l) values obtained in year 2001 reveal 2000) for inland waters, and are significantly influenced
higher concentration from stations 14–20 and could be by inputs from land based sources and regions of indus-
due to intrusion of seawater in different volumes (Tripa- trial catchments. This suggests that the main catchment
thy et al., 1990) and by biological uptake and precipita- area of freshwater entering the creek is practically small,
tion (Ghosh et al., 1991). The observed deviations and the downstream side of the creek is loaded with a
during both the years in Ca2+ and Mg2+ values could high anthropogenic burden. The present trend of toxic
be related to dilution with the effect of estuarine water in- metals (Cr, Cu, Ni, Co, Pb, Zn, Cd) concentration dis-
put playing a major role. Both Ca2+ and Mg2+ in the En- plays a critical trend on the downstream side (stations
nore Creek indicate a conservative behaviour on the 1–12) showing differences from the upstream samples
upstream side similar to that reported elsewhere (Narve- near the mouth region (stations 13–20). The high con-
kar and Zingde, 1987; Ramanathan et al., 1988). Factor centrations and the difference in trends indicate that
analysis reveals that Na+, K+, Ca2+, Mg2+ are dominant they are related to high temperature (due to the thermal
in F1 along with salinity where ion exchange processes power plant). These trends are quite different from those
play a major role in the study area. observed in which the toxic elements increased linearly
Iron distribution in the present study indicates very with distance towards the sea in other creek regions
high values at stations 1–6 (1797–5835 lg/l) on the wes- (Kim et al., 1996).
tern side of the creek, whereas the other stations within The present concentration of trace metals in the
the high salinity zone indicate lower values (Fig. 2m). downstream side indicates adsorption of these metals
This indicates that colloidal flocculation also removes onto suspended matter in the low salinity zone as re-
phosphate as shown by the positive correlation in 2000 ported by many authors (Bewers and Yeats, 1978; Dun-
(r = 0.76) and moderate correlation in 2001 (r = 0.21). iker and Nolting, 1982; Ackroyd et al., 1986). The high
The increase in relationship is seen with high pH where concentration of metals in the mid creek in salinity-mix-
iron is precipitated on the downstream side (stations 1– ing zone is due to the high turbidity of water column and
6), whereas it is removed at the mouth of the creek (sta- from input of effluents from the thermal power plant
tions 18–20). Manganese concentration in the study area (Morris, 1986). In Ennore Creek, the toxic dissolved
reveals a conservative behaviour with high values at low trace metals flocculate principally at high salinities
salinity regions (Fig. 2n). This indicates that active Mn (>28&) and higher salinities in the mixing zone. The dis-
removal has taken place on the downstream side leading tribution pattern is uniform for all the toxic metals (Cr,
to precipitation and high concentration of dissolved Mn Ni, Co, Pb, Zn, Cd), except for Cu, which tend to floc-
(stations 1–7) (Sunda and Huntsman, 1987). Mn is en- culate at intermediate salinity along with Fe and Mn
riched by a factor of three at low salinity (17.8&) than (Sholkovitz, 1976). The negative correlation of pH and
in higher saline (35.8&) creek waters. This indicates that salinity with trace metals and the domination of Cu,
588 Baseline / Marine Pollution Bulletin 50 (2005) 583–608
Pb, Co, Zn in F3 indicate that these metals are not con- Boyle, E.A., Collier, R., Dengler, A.T., Edmonds, J.M., Ng, A.C.,
trolled by pH or salinity. They also suggest that a major Stallard, R.F., 1974. On the chemical mass balance in estuaries.
Geochim. Cosmochim. Acta 38, 1719–1728.
fresh water source is negligible to the Ennore Creek Bridgman, H.A., 1992. Evaluating rain water contamination and
(Kuwabara et al., 1989). The association of these metals sources in southwest Australia using factor analysis. Atmos. Env.
separately in F3 also indicates that the particle bound Gen. Top. 26A, 2401–2412.
trace metals may be desorbed as salinity increases in Brockmann, V., Billen, M., Giekas, W.W.C., 1988. North sea nutrients
the mixing zone (Salomons, 1980; Li et al., 1984; Ack- and eutrophication. In: Salomons, W., Bayne, B.L., Duursma,
E.K., Förstner, U. (Eds.), Pollution of the North Sea: An
royd et al., 1986). This is clearly evident from the inter- Assessment. Springer-Verlag, pp. 17–32.
mediate stations that show higher concentrations of all Byrd, J.T., Lee, K.W., Lee, D.S., Smith, R.G., Windom, H.L., 1990.
metals. The behavior of trace metals in the Geum estuary, Korea. Estuaries
The present baseline data on physico-chemical 13, 8–13.
parameters and metal concentrations in water indicates Callaway, R.J., Specht, D.T., Ditsworth, G.R., 1988. Manganese and
suspended matter in the Yaquina estuary, Oregon. Estuaries 11,
that the local environment is totally different from any 217–225.
known natural ecosystem, and it cannot be compared Church, T.M., 1986. Biochemical factors influencing the residence time
or applied to other areas. The resulting ‘‘cocktail’’ of of micro constituents in a large tidal estuary, Delaware Bay. Mar.
industrial effluents with the creek waters is so complex Chem. 18, 393–406.
that it is practically impossible to predict the chemical Clark, J.F., Simpson, H.J., Bopp, R.F., Deer, B., 1992. Geochemistry
and loading history of phosphate and silicate in the Hudson
behaviour of heavy metals in it and that long term mon- estuary. Estu. Coast Shelf Sci. 34, 213–233.
itoring should be done. However, the existing data Culkin, F., Cox, R.A., 1966. Sodium, potassium, magnesium, calcium
clearly demonstrates that the level of heavy metal con- and strontium in seawater. Deep-sea Res. 13, 789–804.
tamination is high in the Ennore Creek region and that Duniker, J.C., Nolting, R.F., 1982. Dissolved copper, zinc and
the creek acts as an efficient trap for anthropogenic cadmium in the southern bight of the north sea. Mar. Poll. Bull.
13, 93–96.
heavy metals. Despite these high concentrations, devel- Flegal, A.R., Smith, G.J., Gill, G.A., Sanudo-Withelmy, S., Anderson,
opment and expansion of industries are still continuing. L.C.D., 1991. Dissolved trace element cycles in S.F bay estuary.
The present data certainly justifies the need to take up a Mar. Chem. 36, 326–363.
detailed study on the impact of higher concentration of Ganapathi, P.N., Raman, A.V., 1973. Pollution in the Visakhapatnam
trace metals on the coastal eco-system along Ennore Harbour. Curr. Sci. 42, 490–492.
Ganapathi, P.N., Raman, A.V., 1979. Organic pollution and skeleto-
Creek, southeast coast of India and any remedial action nema blooms in Visakhapatnam harbour. Indian J. Mar. Sci. 8,
should be taken at the earliest. 184–187.
Ghosh, S.K., De, T.K., Choudhury, A., Jana, T.K., 1991. Oxygen
deficiency in Hoogly estuary, east coast of India. Indian J. Mar.
Sci. 20, 216–217.
Acknowledgments Hall, J.A., Frid, L.J.C., Proudfoot, R.K., 1996. Effects of metal
contamination on macro benthos of two North sea estuaries. ICES
The study forms part of the DST-FIST program J. Mar. Sci. 53, 1014–1023.
Hydes, D.J., Edmonds, H., 1989. Qualitative assessment of nutrient
awarded to Department of Geology and Applied Geol-
measurements. Institute of Oceanographic Sciences, NERC
ogy, University of Madras and University Grants Com- Report, 269p.
mission-Special Assistance Programme (Phase II) and Kim, J.P., Reid, M.R., Cunninghame, R.G., Hunter, K.A., 1996.
COSIST program awarded to Department of Geology, Aqueous chemistry of major ions and trace metals in the
University of Madras. The authors thank Dr. B.J. Rich- Clutha river, New Zealand. Mar. Fresh Water Res. 47, 919–
928.
ardson and Dr. N. Rajeshwara Rao for fine-tuning the
Knox, S., Turner, D.R., Dickson, A.G., Liddicoat, M.I., Whitefield,
manuscript. M., Butter, E.I., 1981. Statistical analysis of estuarine profiles:
application to manganese and ammonia in the Tamar estuary.
Estu. Coast Shelf Sci. 13, 357–371.
Kuwabara, J.S., Chang, C.C.Y., Cloern, J.E., Fries, T.L., Davis, J.A.,
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0025-326X/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2005.01.021
a
School of Environmental Engineering, Faculty of Environmental Sciences, Griffith University, Nathan, QLD 4111, Australia
b
CRC for Coastal Zone, Estuary and Waterway Management, Indooroopilly Sciences Centre, 80 Meiers Rd, Indooroopilly, QLD 4068, Australia
c
School of Australian Environmental Studies, Faculty of Environmental Sciences, Griffith University, Nathan, QLD 4111, Australia
Anthropogenic contaminants introduced into the trace metal bioavailability in sediments is controlled by
aquatic environment can eventually accumulate in ben- sorption to several solid-phases (such as iron oxyhy-
thic sediments. Sediment quality assessment is therefore droxides, organic matter and reactive sulfide species;
an important consideration in ensuring the ecological Chapman et al., 1998). Furthermore, total metal analy-
sustainability of coastal regions. An important research sis often provides a poor indication of bioavailability
focus associated with sediment quality assessment is and potential mobility (ANZECC/ARMCANZ, 2000).
determining whether sediments enriched with trace met- As such, the use of partial extractions potentially pro-
als actually exert an adverse effect on aquatic ecosystems vides a more accurate representation of the concentra-
(Ankley et al., 1994). This issue is complicated because tion of reactive, bioavailable metal species (Burton
et al., 2005).
The use of 1 M HCl as a measure of the reactive me-
*
tal fraction has recently been recommended by AN-
Corresponding author. Address: School of Environmental Engi-
ZECC/ARMCANZ (2000). Reactive sulfide species are
neering, Faculty of Environmental Sciences, Griffith University,
Nathan, QLD 4111, Australia. Tel.: +61 7 3875 6713; fax: +61 7 known to exert a major control on trace metal behav-
3875 7459. iour in anoxic sediments and their measurement may
E-mail address: e.burton@griffith.edu.au (E.D. Burton). assist in the interpretation of 1 M HCl-extractable metal