Indian Journal of Geo-Marine Sciences Vol. 44(9), September 2015, pp. 1310-1322

Dynamics and quantification of dissolved metals in a highly contaminated river-estuarine system

S.C. Asa1, S.N. Bramha2, A.K. Mohanty2, T.K. Bastia1, D. Behera1 & P. Rath1*

1 *School of Applied Sciences, Department of Chemistry, KIIT University, Bhubaneswar, Odisha. 2Radiological Safety and Environmental Group, Indira Gandhi Centre for Atomic Research (IGCAR), Department of Atomic Energy, Govt. of , Kalpakkam-603 102, Tamil Nadu, India. *[E-Mail: [email protected]; [email protected]]

Received 04 July 2014; revised 11 September 2014

Dynamics of heavy metals such as Fe, Mn, Co, Ni, Cu, Zn, Cr, Pb and Cd in surface water of -estuarine system were studied taking 25 samples from different sampling locations along the complete stretch. Irrespective of season, Fe was most abundant in both river (avg. 260.15 µg / l ) and estuarine (avg. 119.9µg / l) samples, whereas Cd (avg. 1.59 µg / l) and Co (avg.1.55µg / l) were the lowest in the river and estuarine samples respectively. The average concentrations of all the dissolved metals were much higher than the world river average. The average concentrations Cr and Cd for the river were above the criteria of maximum concentration (CMC) as prescribed by US Environmental Protection Agency. Results of factor analyses revealed that anthropogenic contributions were the source for the increase in dissolved metal concentrations. Canonical discriminate function indicated that it was moderately successful in discriminating the groups as predicted. River Brahmani with an annual discharge of 18.58 x 10 m carries 6.907 x 10 tons of total heavy metals into Bay of and the calculated rate of erosion in the basin is 176.582 kg km year.

[Keywords: Dissolved metals, Enrichment ratio, Metal Pollution Index, Discriminate analysis, Factor analysis] Introduction Rivers play a major role in assimilating changes such as dissolution, precipitation, heavy metals from both natural sources through sorption, complexation etc, which affect their erosion, weathering of source rock and bio-availability6. anthropogenic sources such as urban sewage Though many works have already been carrying domestic wastes, effluents from reported pertaining to geochemistry, hydro geo- different industries, washings from agricultural chemistry and water quality of Brahmani River7- fields containing fertilizer and pesticides1 and 12, most of those studies focused on small from mining areas through various ways such as stretches of the river or some specific areas and mine discharge, run-off, dissolution of rocks and in addition concerned with physico-chemical soils, wet and dry fallout of atmospheric parameter of river water and metal distribution particulate matter etc2-4. in sediments. No attempt has been made so far Metals such as Cu, Zn etc are essentially regarding dissolved metal distribution along the required by different living species in water complete stretch of the river including the bodies. However nutritional requirement of estuary and near shore area. In the present study, these metals substantially differ from species to concentrations of some selective heavy metals species and that is too in a narrow range. (Fe, Mn, Co, Ni, Cu, Zn, Cr, Pb and Cd) in Exposure to elevated concentration of metals surface water of Brahmani river-estuarine may result in serious consequences such as death system were measured. A quantitative approach of certain species. High levels of heavy metals has been made by the use of enrichment ratio, also cause metal accumulation by aquatic metal pollution index (MPI) and through organisms affecting the species higher up in the comparison with standards for surface water food chain. In addition some metals like Cr, Cd, quality and levels for the same in other studies Pb etc are highly toxic even at very low level5. of India and World. Individual metal loads were In river water metals exist in two forms i.e. also calculated. Multivariate statistics such as suspended particulate and dissolved forms. factor analysis was applied for meaningful data During transportation they undergo numerous reduction and interpretation of results.

ASA et al.: DYNAMICS AND QUANTIFICATION OF DISSOLVED METALS IN A HIGHLY CONTAMINATED RIVER-ESTUARINE 1311 SYSTEM

Discriminate analysis was performed for Table 1 Anthropogenic scenario of the basin discrimination of sampling sites with respect to the measured parameters. Industry Product/s Water Pollutants Waste Consumption water [m3/ day ] generated Materials and Methods [m3 / day ] Agricultural Fertilizers, 405.6 M Brahmani River is the second largest river in run-off pesticides, m3/year Odisha having drainage basin of 39,035 km2 - - nutrients, SS,TDS, area with total length of 800 km and peak heavy metals discharge of 22,640 m3 s-1. It mixes with River Industrial & Oil, grease, 90,000 Urban heavy Baitarani to form Dhamara estuarine system townships, metals, - - before meeting the Bay of Bengal. Brahmani major urban nutrients, SS, centers and TDS River receives effluents from most of the major conglomerates industries of Odisha located in Rourkela, Angul, Rourkela Steel Iron and Steel 2,65,580 Heavy 1,20,000 Plant [RSP] metals, SS, Talcher and Jajpur Industrial areas, washings oil, grease from mines located in Angul-Talcher belt and RSP Fertilizer 28,807 Nutrient, 7,920 [CAN] Heavy metal Sukinda, sewage from a number of major Fertilizer Fertilizer 45,883 Heavy 16,608 townships along with agricultural runoff from its Corporation of [Urea] metals, SS, India oil, grease catchment area. As a result, the river water does NALCO Aluminium 5,066 4,900 not represent a healthy aquatic ecosystem. The [Smelter] NALCO [CPP] Electric 1,35,000 90,000 detailed basin status with respect to source of power generation of waste water, volume of waste ORICHEM Ltd Na2Cr2O7, 170 10 Basic water generated, water consumption by major Chromium industries, important pollutants is summarized in Sulphate, Yellow Table 1. The basin lies in an Indian shield that sodium consists of Pre-Cambrian rocks such as granites, sulphate Talcher Electric 13,227 6,483 gneisses, quartzites, schists of Eastern Ghats, Thermal power power amphibolites, pegmatites, khondalites and Talcher Electric 1,37,099 52,080 Thermal Power power charnockites and Gondwana rocks like shale, Plant, NTPC, Heavy sandstone and coal11. This basin of Odisha is of Kaniha metals, SS, MESCO Iron Iron and Steel 84,840 oil, grease 40,078 high environmental importance due to the Steel Ltd. presence of mangrove forest ecosystem, Bhusan Steel Iron and Steel 2,29,200 1,08,274 Ltd. Bhitarakanika National Park, a Wild Life Brahmani Steel Iron and Steel 84,840 40,078

Sanctuary which has been listed as a RAMSAR ORIND Steel Iron and Steel 16,800 7,936 site in 2002, crocodile breeding centre and the Ltd. Neelachal Steel Iron and Steel 1,75,200 82,764 Olive Ridley nesting beaches. This basin also Ltd. has a considerable potential for development of Jindal Steel & Iron, Steel - - Power and Electric inland fisheries in reservoirs, ponds, tanks and Power canals. Mines: Coal, iron and - - In order to monitor the dissolved metal chromite mines concentration, water samples from 25 stations were collected along the complete stretch of the eight are from saline water zone which includes river between Feb-May (dry season) and July- estuary and coastal sea up to a distance of 3 km Oct (wet season) as shown in Figure 1. Out of from shore. Stations were selected on the basis these stations 17 are from fresh water zone while of location of major industries, municipal- township discharge points and also on accessibility to the sampling sites. In each station sampling was carried out for five times during the sampling period and average value was taken for evaluation. Surface water samples were collected from the mid stream of the river and at a depth of 20-30 cm from water surface. To minimize the contamination from boat

1312 INDIAN J. MAR. SCI., VOL. 44, NO. 9 SEPTEMBER 2015

Figure 1 Map showing sampling locations wherever used and also from the surface, the and accuracy of the methods were systematically samples were collected by travelling in upstream and routinely checked by analyzing standard direction. Acid cleaned, dried polythene solutions procured from Merck after desired containers were used for this purpose. dilutions. After collection pH was measured Multivariate statistical analysis was performed immediately by a portable battery operated pH through factor and Discriminate analysis meter (Elico- Model No. DI-707). DO was techniques16,17. Factor analysis was performed measured by Winkler’s titration method. One on correlation matrix of rearranged data of the liter of river water was filtered through 0.45 mm dissolved metal concentrations, pH and DO. The Millipore cellulose nitrate filter paper using a variance and factor loadings of the variables vacuum pump. The filtered water samples were with eigen values were computed. Stepwise acidified by concentrated HNO3 to bring down Discriminant analysis using Wilks’ method was the pH around 2.0, so as to inhibit adsorption of carried to investigate differences between the metal ions on to container surface and to prevent groups on the basis of the variables of the cases, metal precipitation. The concentrations of Fe, indicating which variables contribute most to the Mn, Co, Ni, Cu, Zn, Cr, Pb and Cd metal ions in group separation and in addition to test the the pre-concentrated solutions were determined theory whether cases are classified as predicted. with the help of Atomic Absorption Data were processed using routines taken from Spectrophotometer (AAS) model Perkin Elmer Statistical Program for Social Sciences (SPSS- 1025. Pre-concentration was made by non- Version 20.0) statistical software. boiling evaporation13 except for samples taken from saline water zone where chelating solvent- Results and Discussion extraction technique was adopted. The Minimum, maximum, mean and standard concentrations of metal ions were measured deviation for concentrations of the analyzed after ammonium pyrolidine dithiocarbamate heavy metal ions along with pH and DO in water (APDC)-methyl isobutyl ketone (MIBK) samples of Brahmani river-estuarine system are extraction14. Because of the instability of the reported in Table 2, while the detail spatial complexes with metals like Mn, the metals were variation is given in Figure 2. The dissolved again back extracted to aqueous medium with metal concentrations in Brahmani river estuarine 15 HNO3 before analysis. Milli-Q water was used system, other rivers in India/World, World River throughout the analysis. The analytical data averages along with drinking water standards quality was ensured through careful and maximum permissible limits prescribed by standardization, procedural blank measurements, different agencies are depicted in Table 3. spiked and duplicate samples. The precession ASA et al.: DYNAMICS AND QUANTIFICATION OF DISSOLVED METALS IN A HIGHLY CONTAMINATED RIVER-ESTUARINE SYSTEM 1313

Table 2 Descriptive statistics of dissolved metal concentrations along with pH and DO in Brahmani river estuarine system during Dry and Wet season.

Dry Season Wet Season

Parameter Units Fresh Saline Fresh Saline Min. Max. Mean Std. Dev. Min. Max. Mean Std. Dev. Min. Max. Mean Std. Dev. Min. Max. Mean Std. Dev.

pH - 7.10 8.90 7.98 0.55 7.94 8.37 8.18 0.14 7.50 9.00 8.40 0.44 8.45 8.91 8.67 0.15 DO / 5.84 9.44 7.80 1.08 6.08 8.14 7.40 0.61 7.20 10.30 8.71 0.78 7.87 8.80 8.33 0.38 Fe µ/ 110.23 545.53 244.35 116.23 32.80 200.32 117.08 70.05 120.50 560.32 275.94 119.40 30.70 205.78 122.72 69.17 Mn µ/ 5.87 27.36 11.64 5.64 1.35 9.40 5.61 3.53 8.90 30.32 16.45 6.45 1.97 13.30 7.49 4.66 Co µ/ 2.18 13.56 6.23 3.36 0.73 3.50 1.63 1.04 2.00 10.20 5.34 2.62 0.60 3.24 1.47 0.99 Ni µ/ 4.24 31.92 12.80 6.79 1.34 8.50 3.29 2.50 4.10 28.45 11.30 6.14 0.96 6.35 2.79 1.95

Cu µ/ 1.40 41.00 12.25 11.90 2.75 22.70 10.56 8.42 1.15 38.20 11.01 11.09 2.38 18.38 9.24 7.28 Zn µ/ 10.30 48.08 22.06 8.64 10.87 20.70 16.26 3.63 9.40 45.65 20.08 8.72 10.20 19.33 15.58 3.42 Cr µ/ 9.90 165.78 43.65 40.48 5.06 35.70 15.60 11.01 7.80 135.40 38.39 33.51 4.80 31.43 14.63 9.58 Pb µ/ 1.28 9.87 4.75 2.28 1.15 8.80 3.80 2.82 1.12 8.50 4.21 1.92 0.92 7.72 3.36 2.47 Cd µ/ 0.12 4.40 1.69 0.95 1.85 3.52 2.81 0.56 0.10 3.98 1.48 0.89 1.63 3.87 2.90 0.70

Table 3 The dissolved metal concentrations in Brahmani river estuarine system along with other rivers in India/World and the World River average.*Martin and Whitfield, 1983[44].

Rivers Fe / Mn / Co / Ni / Cu / Zn / Cr / Pb / Cd / References

Ganga river 48998.00 7.72 - 58 36.00 115.00 - 25.00 0.14 [18] Cauvery 9.90 2.60 - 38.30 6.00 81.60 48.80 1.36 0.43 [19] Godavari 7.50 - - 0.14 0.92 0.66 - 5.60 0.07 [20] Kali River 51000.00 3.95 0.70 0.80 1.34 10.03 - 0.70 0.13 [21] Hindon River 226.00 129.00 24.00 6.60 58.00 15.00 37.00 - [22] Mahanadi River 189.38 19.88 3.62 10.19 8.39 29.28 3.67 8.04 0.91 [23] 66.25 11.38 1.13 15.75 15.88 23.00 1.13 19.13 - [24] Han River, Chaina 30.64 30.72 2.24 1.71 13.35 - 8.14 9.26 2.31 [25] Tigris River, Iraq 835.00 27.9 - 5.11 2.11 2.78 3.67 0.48 0.02 [26] Brahmani River 260.15 14.05 5.79 12.05 11.63 21.07 41.02 4.48 1.59 This Study

World River Avg. 55.00 6.00 0.20 0.30 1.00 10.00 0.50 0.20 0.02* [27] BIS, IS: 10500 [28] 1,000 300 - - 1,500 15,000 50 50 10

WHO[29] 1,000 500 - 20 2,000 5,000 50 10 3

USEPA, 2009 [30] 300 50 - - 1,300 5,000 100 15 5 water ng standard standard

CMC, USEPA, 2006 [31] - - - 470 13 120 16 65 2 Drinki

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Among the heavy metals the most abundant 30.32 µg/l in river and 1.97-13.30 µg/l in saline one was Fe in both fresh and saline water zone, water zone. Higher average of both the metals in whereas, Cd and Co appeared as least abundant rainy season may be attributed to lower pH of at fresh and saline water zone respectively, rain water as compared to river water average, irrespective of seasons. Mean concentrations of which might be responsible for weathering of different metals in fresh water and saline water these metals from surface. Lower average zone followed the order Fe> Cr> Zn> Mn> Ni> concentration observed in saline water than that Cu> Co> Pb> Cd and Fe> Zn> Cr> Cu> Mn> in fresh water zone could be attributed to Pb> Ni> Cd> Co respectively. As expected, the precipitation of these metals to their hydroxides average concentration of metals in estuarine under alkaline pH condition of estuary34. The saline water zone was found to be less than that highest value of Fe is reported at BR_7 i.e. D/S of the river fresh water zone, which could be of Angul-Talcher industrial complex followed attributed to different geochemical processes by BR_2 i.e. D/S of Rourkela, irrespective of that help in the removal of dissolved metals seasons. This could be attributed to the effluents from water column. Primary processes include of metallurgical industries and thermal power flocculation of dissolved organic matter in plants. For manganese the highest value is complexation with dissolved metals at low reported at BR_2. The complete spatial variation salinity zone, adsorption onto suspended matter in both seasons is shown in Figure 2. The which dominates the processes with increasing average concentrations of both the metals are pH gradient and adsorption onto freshly much higher than World River Average 27, precipitated Fe and Mn oxy-hydroxide coatings however remains well within the limits of on mineral grains. It has been observed that drinking water standard prescribed by BIS organic precipitation and adsorption of heavy 199128 and WHO 200429. metals to fine particles is prominent in estuarine Co (II) is observed to be the dominant zone, while adsorption onto freshly precipitated species of cobalt in fresh water. Cobalt Fe and Mn oxy-hydroxide coatings on mineral concentration in uncontaminated surface water is grains seem to dominate the proceedings in generally very low, usually < 1 μg/l. The coastal zone7. The role of dilution also can’t be concentration of Co was found to be 2.18-13.56 ignored. With respect to temporal variation the µg/l with an average of 6.23 µg/l and standard average concentration of all metals except Fe deviation 3.36 in the fresh water area and 0.73- and Mn decreased in wet season. This might be 3.50 µg/l with an average of 1.63 µg/l in saline due to dilution effect in high flow conditions as water zone during dry season. Similarly during it is a monsoon fed river. The detail spatial and wet season it varied in the range 2.0-10.20 µg/l seasonal variation of different metals has been with an average of 5.34 µg/l in fresh water area discussed as follows. and 0.60-3.24 µg/l with an average of 1.47 µg/l The concentration of iron in Brahmani river in the estuary. These values are quite higher than water lies within 110.23-545.53 µg/l during the world river average value (0.2 µg/l). summer and 120.50- 560.32 µg/lin rainy Irrespective of seasons, the highest seasons with an average of 244.35 and 275.94 concentration was reported at BR_2 i.e. D/S of µg/l respectively. In saline water zone the Rourkela which may be attributed to municipal concentration ranged from 32.80- 200.32 µg/l sewage as well as industrial wastes from with an average 117.08 µg/l during summer and Rourkela industrial complex that mix-up with 30.70-205.78 µg/l with an average of 122.72 main stream of river before this sampling site. µg/l during rainy season. In neutral to slightly The complete spatial variation is shown in basic waters of the Brahmani River dissolved Figure 2. Mn mostly remain as Mn (II) which readily react Ni (II) is the most stable oxidation state of with carbonates and bicarbonates32. Manganese Ni which is stable over a wide range of pH. As (II) carbonates is expected to play an important most of the nickel salts are readily soluble, they role in distribution of dissolved Mn in interstitial can easily contribute to water pollution through waters of river33. Its concentration varies within municipal and industrial waste discharge35. The 5.87-27.36 µg/l with an average of 11.64 µg/l Ni concentration varied from 4.24-31.92 µg/l in river and 1.35-9.40 µg/l with an average of with an average of 12.80 µg/l in river and 1.34- 5.61 µg/l in saline water during summer. During 8.50 µg/l with average of 3.29 µg/l in estuary rainy season Mn concentration varied from 8.90-

ASA et al.: DYNAMICS AND QUANTIFICATION OF DISSOLVED METALS IN A HIGHLY CONTAMINATED RIVER-ESTUARINE 1315 SYSTEM during dry season. Similarly, its concentration ranged from 4.10-28.45 µg/l with an average of

600 Summer 25 500 Rainy 20 400 15

g/l) 300 m ( g/l) 10

200 m Fe ( 100 5 Co 0 0 SR SR BR_01 BR_03 BR_05 BR_07 BR_09 BR_11 BR_13 BR_15 DE_02 DE_04 DC_02 DC_04 BR_01 BR_03 BR_05 BR_07 BR_09 BR_11 BR_13 BR_15 DE_02 DE_04 DC_02 DC_04

40 60 35 50 30 25 40 g/l)

20 g/l) 30 m m ( 15 ( 20 Mn

10 Zn 5 10 0 0 SR SR BR_01 BR_03 BR_05 BR_07 BR_09 BR_11 BR_13 BR_15 DE_02 DE_04 BR_01 BR_03 BR_05 BR_07 BR_09 BR_11 BR_13 BR_15 DC_02 DC_04 DE_02 DE_04 DC_02 DC_04

8 50 7 40 6 5 30

g/l) 4 m ( g/l) 20 3 m (

Cd 2

Ni 10 1 0 0 SR SR BR_01 BR_03 BR_05 BR_07 BR_09 BR_11 BR_13 BR_15 BR_01 BR_03 BR_05 BR_07 BR_09 BR_11 BR_13 BR_15 DE_02 DE_04 DE_02 DE_04 DC_02 DC_04 DC_02 DC_04

60 14 50 12 10 40 8 g/l) g/l

30 m

( 6 ( m 20

Pb 4 Cu 10 2 0 0 01 03 05 07 09 11 13 15 02 04 SR SR _02 _04 BR_ BR_ BR_ BR_ BR_ BR_ BR_ BR_ BR_01 BR_03 BR_05 BR_07 BR_09 BR_11 BR_13 BR_15 DE_02 DE_04 DE_ DE_ DC DC DC_02 DC_04

200

150 g/l)

m 100 (

Cr 50 Figure 2 Spatial variations of dissolved 0 metals along Brahmani river-estuarine SR DE… DE… DC… DC… system. BR_01 BR_03 BR_05 BR_07 BR_09 BR_11 BR_13 BR_15

1316 INDIAN J. MAR. SCI., VOL. 44, NO. 9 SEPTEMBER 2015

11.30 µg/l in river and 0.96-6.35 µg/l with river estuarine system is well within the average of 2.79 µg/l in estuary during wet prescribed limits of CMC31, drinking water season. Irrespective of seasons, the highest value standard by BIS28 and WHO29. Irrespective of was observed at BR_2, the D/S of Rourkela. seasons, the highest value is reported at BR_2 High values are also reported at D/S of industrial followed by BR_7. This may attributed to the conglomerates and major towns which may be processing ferrous ores, municipal sewage and attributed to the urban waste water, smelting and seepage from municipal dumping in up-stream burning of fossil fuel particularly coal in thermal areas of these locations. Due to basic conditions power plants. The mean concentrations of Ni in in Brahmani river and estuary (average pH is Brahmani River as well as in estuary region ~ 8 or more), Zn remained effectively were observed to be much higher than world immobilized in all redox conditions39. This fact river average (0.3 µg/l) and other Indian rivers. is well reflected in the spatial variation. However it is within the criteria of maximum Chromium concentration in natural water is concentration (CMC) as prescribed by USEPA, usually very small, however high concentration 200631 limit (470 µg/l) and WHO limit can result from industrial and mining process40. (20 µg/l ). However the concentration at some Enrichment of Cr particularly at stations BR_9 stations like BR_2 and BR_7 is higher than and BR_10, the D/S stations of Sukinda, which WHO standard. is one of the largest chromite reservoirs of the Copper occurs in water in different forms country, was observed in the present study. The like Cu-humic acid complex36. Concentration of mine drainage of the area is discharging through Cu in river Brahmani varied within 1.40-41.00 Damsala Nala which is a tributary of Brahmani µg/l in dry and 1.15-38.20 µg/l in wet seasons. River near Bhuban. In Brahmani River, In saline water zone it varied within 2.75-22.70 concentration of Cr varied from 9.90-165.78 µg/l and 2.38-18.38 µg/l during dry and wet µg/l with an average of 43.65 µg/l during seasons respectively. The concentration of Cu summer and 7.80-135.40 µg/l with an average was much higher than world river average and of 38.39 µg/l during rainy season. The mean other Indian rivers. In many stations the values concentrations were much higher than world were also above the drinking water CMC31 but river average (0.5 µg/l27, and CMC limits within the limit of BIS28 and WHO29. 16 µg/l31). The concentration of dissolved Cr Irrespective of season the highest value was decreased towards sea, which could be due to reported at BR_11 i.e. D/S of Jajpur industrial the increase in distance from source, dilution of conglomerate. In general the high values were fresh water with sea water41 in addition to the recorded in coastal plain stations. High level of other geo-chemical processes as mentioned Cu in the study area could be the contribution of above. Municipal effluents and leachates from solid The concentration of Pb varied within 1.28- waste of Rourkela, Angul-Talcher, Sukinda 9.87 µg/l and 1.15-8.80 µg/l in river and industrial and mining areas. In addition high estuary during dry season while 1.12-8.50 µg/l dissolved Cu in coastal plain sediments may be and 0.92-7.72 µg/l in river and estuary during attributed to extensive use of fertilizers and rainy season. The highest value of Pb (9.87 µg/ fungicides in agriculture. The same is well l) was reported at Kamalanga the D/S of Angul- reflected in the spatial variations (Figure 2). Talcher industrial and coal mining area. This Though the mean concentration in estuary is less might be through atmospheric deposition of than the river, still some mobilization is marked aerosols containing Pb from coal mining sites. during initial mixing of fresh and saline waters. Lead is also contributed through discharge of Several workers such as Vazquez et al.37, Muller solid wastes such as Pb batteries, PVC plastics, et al.38 have also reported the same observations. paints, alloys etc by the urban setups in and As per Muller et al.38 it may be due to formation around the study area. In dry season the second of organo-copper complexes in saline water. highest concentration is noticed at D/S of The Zn concentration in Brahmani River Sukinda which is again an extensive mining site. was 10.30-48.08 µg/l and 9.40-45.65 µg/l In addition thousands of trucks are utilized here during dry and wet seasons respectively. for transportation of ore which is the only Irrespective of seasons, the Zn concentration at conveyance. The Pb concentration in river all sampling sites were above world river Brahmani is within the limits of CMC31; average of 10 µg/l27. Zn content in Brahmani drinking water IS: 10500, by BIS28 and WHO29.

ASA et al.: DYNAMICS AND QUANTIFICATION OF DISSOLVED METALS IN A HIGHLY CONTAMINATED RIVER-ESTUARINE 1317 SYSTEM However, it is above the world river average the sampling sites are having values value of 0.20 µg/l27. corresponding to this value of ER for a specific Cd enters into the natural hydrological metal. The ‘whiskers’ above and below the box system through aerosol deposition, agricultural show the locations of the minimum and field washings as well as through dumping of maximum values of ER. Outliers are noticed for untreated effluents by industries42. The dissolved Ni and Cr in the upper side. The outlier in case Cd concentration in fresh and saline water zones of Ni is due to abnormally high ER at site BR_2, was reported as 0.12-4.40 µg/l and 1.85-3.52 D/S of Rourkela sector while the same for Cr is µg/l during dry and 0.10-3.98 µg/l and 1.63- due to abnormally high ER at site BR_9, BR_10 3.87 µg/l during wet season. The temporal and BR_11 the D/S stations of Sukinda. Outliers variation of Cd among sampling sites was are presented as asterisks and are greater than insignificant. Relatively high values of dissolved 1.5 times of interquartile distance from each Cd were observed at Rourkela D/S (BR_2) and quartile. ER values in different sampling sites Kamalanga, D/S of Angul-Talcher industrial ranges from 0.6 to 1.1 for Fe, 0.3- 4.8 for Mn, zone (BR_7), irrespective of seasons, which 3.3-59.4 for Co, 3.8-100.6 for Ni, 1.3-39.6 for could be attributed to the direct input from Cu, 1.0-4.7 for Zn, 9.9-301.2 for Cr and 5.2-45.9 metallurgical, fertilizer industries and urban for Pb. The above result showed enrichment of sewage of the industrial townships. The high all the metals in the study area, which is mainly value of Cd in some coastal stations may be due due to the mining and industrial activities. to the extensive use of phosphatic fertilizers in 350 43 agriculture which are reported to contain Cd . 300 The observed values are well above the world river average of 0.02 µg/l44. The average 250 concentration of Cd in saline water is more than 200 CMC as prescribed by USEPA31 in both dry and 150 wet seasons. Except BR_2 and some coastal nge Ra stations the values are within the limit as 100 prescribed by WHO29 for drinking water. Some mobilization in distribution of Cd is observed in 50 estuarine region. It may be due to chloride and 0 sulphate complexation in addition to ionic strength effects resulting in Cd desorption from -50 sediments45. Fe Mn Co Ni Cu Zn Cr Pb Cd Figure 3 Box–whisker plots showing Metal enrichment ratio enrichment factors for dissolved metals in the Metal enrichment as a result of contamination study area can be estimated in a number of methods. Metal Pollution index Different authors have compared their data Metal Pollution index (MPI) represents the pertaining to a particular environment with that composite influence of all metals on the river of similar environment in other places of the water quality46. The MPI represents the sum of country/world. In the present study, a method the ratio between the concentration of analyzed called enrichment ratio (ER) analysis has been metal and their corresponding maximum used to quantify the enrichment of heavy metals allowable concentrations (MAC). The drinking of the study area. Here comparison has been water standards of India28are used as MAC for made with respect to global background values. the metals, with the exception of Co and Ni for World river average of dissolved metals is used which BIS28 does not provide a standard. as global background concentration27. ER > 1 is Instead, the New York State Department of termed as enrichment while ER < 1 represents Environmental Conservation (NYSDEC) water depletion with respect to Global background. quality standard for Co (5 µ/) was used and The ER for the dissolved metals (average for Ni, CMC as prescribed by USEPA31 was concentration of both dry and wet season) in the used. study area has been presented in box-whisker plot (Figure 3). The small box inside MPI = ∑ () th corresponds to the mean value while the line in Where, C = Concentration of ‘i ’ metal. the box corresponds to the median i.e. 50% of MAC = Maximum allowable concentrations.

1318 INDIAN J. MAR. SCI., VOL. 44, NO. 9 SEPTEMBER 2015

A six category ranking system is used to stations.stations. The water from stations BR_2, Br_9 express the degree of anthropogenic influence of and BR_10 remains in class V i.e. strongly metals on the water quality and to classify water affected category. BR_2 is the D/S station of quality at different sampling stations47. A MPI of Rourkurkelaela that receives effluents of Rourkela < 0.3 represents very pure (Class I), 0.3 - 1.0 Steel Plant and other small scale industries in the poor (Class II), 1.0 - 2.0 slightly affected (Class Rourkela sector along with the urban sewage of III), 2.0 - 4.0 moderately affected (Class IV), 4.0 the steel city while BR_9 and BR_10 are the - 6.0 strongly affected (Class V) and a MPI of > downstream stations of Sukinda which is one of 6.0 represents seriously affected (Class VI). The the largest chromite resservoirservoirs of the country. MPI values for different sampling stations are These stations mainly receive the mine washings presented in Figure 4. TheThe maximum MPI is along with dry and wet fall out of atmospheric denoted by vertical error bars. The values show particulate matters. The other river stations that among river stations, the station from Sankh along with the stations from estuary remain in river remains in class I along with coastal

6.0

5.0

4.0

3.0

2.0 Pollution Index Pollution 1.0

Metal 0.0 SR BR… BR… BR… BR… BR… BR… BR… BR… BR… BR… BR… BR… BR… BR… BR… BR… DE… DE… DE… DE… DE… KR DC… DC… DC… Locations Figure 4 Metal Pollution Index at differentdifferent sampling sites

slightlyslightly to moderately affected category as far as as ‘strong’, ‘moderate’ and ‘weak’ dissolved heavy metals are concerned. corresponding to absolute loading values of >

Factor analysis Table 4 Factor analysis (All samples as a single group) R-mode factor analysis was carried out to clarify relation among the dissolved metal, pH Rotated Component Matrix and dissolved oxygen DO for 25 locations. A Parameter Component varimax rotation of principal components or F1 F2 F3 factors was used to clarify the picture for Fe 0.937 simpler and more meaningful representation of Mn 0.983 underlyingunderlying factors as it lowers the contribution Co 0.888 to factors of variables with minor significance Ni 0.948 and increase the more significant one. Three Cu 0.780 factorsfactors with eigen value greater than unity Zn 0.917 explaining 82.99 % of the variance or Cr 0.451 0.627 0.441 information contained iinn the original data set Pb 0.604 0.681 was retained. The results of three factors with Cd -0.844 loadings greater than 0.40 for individual pH 0.795 parameters, considering their significant DO 0.866 influence towards the hydro-geochemical Eigen Value 5.023 2.344 1.749 processes, are presented in Table 4. During % Variance 45.781 21.313 15.899 interpretation the factor loadings are classified Cumulative Variance 45.781 67.095 82.994

ASA et al.: DYNAMICS AND QUANTIFICATION OF DISSOLVED METALS IN A HIGHLY CONTAMINATED RIVER-ESTUARINE 1319 SYSTEM 0.70, 0.70–0.50 and 0.50–0.40, respectively48,49. Stepwise discriminate analysis using Wilks’ method was carried out by entering sampling Three factors have been isolated which sites as grouping variables and the metal together explains 82.99 % of the total variance. concentrations as independent variables. The Varifactor 1 represented 45.78% of the total module was executed by entering the most variance and was found to have strong positive correlated variable in the beginning and then the loading of metals like Mn, Ni, Fe, Zn & Co and second and so on until an additional variable moderate positive loading of Pb. This indicates brings no significant change. The summary of that Fe and Mn are effective scavengers of canonical discriminate functions is presented in heavy metals in water column. The strong Table 5. Here, first canonical discriminate loading of metals mentioned reflects their function accounts for 97.9 % while second common source of origin which may be the function accounts only for 2.1 % of the effluents of metallurgical industries and mining discriminating ability of the variables. The activities in the basin. Moderate loading of Pb standardized canonical coefficients indicate that Table 5 Summary of canonical discriminate ‘Cd’ and ‘Pb’ largely contributed to the first functions discriminate function while ‘Pb’ to the second discriminating functions. A very high canonical

Discriminate functions correlation is observed for first discriminating F1 F2 Eigen Function 5.057 0.110 function. A small Wilks’ lambda (0.149) for the % of Variance 97.9 2.1 first discriminating function indicates that it is Cumulative % 97.9 100 moderately successful in discriminating the Canonical 0.914 0.315 groups. The plot of first and second canonical correlation discriminate functions demonstrates the Wilks’ lambda 0.149 0.900 Chi square 86.727 4.769 distinctive groupings (Figure 5). The cross 8 3 validated classification results reveal that 88.0% Significance 0.000 0.190 of cases were classified correctly into river, Variables Standard coefficients estuary and coastal groups. River group was Co -0.763 -0.726 classified with absolute accuracy of 100 %, then Ni -1.414 0.207 coast with 66.7% accuracy and estuary with the Pb 1.131 1.219 Cd 1.305 -0.217 least accuracy of 60 %. shows its independency within the group. The Varifactor 2 represents 21.31% of the total variance and is strongly loaded with Cu and pH. Moderate loading of Pb and Cr in this fraction indicates their common source of origin. This may be through wet and dry fallout of atmospheric particulate matter at mining areas particularly at Sukinda valley, which is considered as one of the major chromite deposits in the country, and coal mines in Talcher belt. The fuel burnt by thousands of trucks utilized here for transportation of ore could also be the source of these metals. Varifactor 3 which accounted for 15.90 % of the variation was found to have strong positive loading of DO and negative loading of Cd. The trend may be attributed to the fact that in oxic condition Cd remain primarily scavenged by non-detrital Figure 5 Plot of first and second canonical carbonate minerals which limits its solubility as discriminant functions 50 Cd . Metal load in the Basin The annual metal load and erosion rate in the Brahmani river basin was calculated using Discriminate analysis average metal content of the nine metals

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considered in this study, the annual water and the calculated rate of erosion in the basin is discharge and drainage area12,51. River Brahmani 176.582 . with an annual discharge of 18.58 x 10 carries 6.907 x 10 of total heavy metals Acknowledgement into Bay of Bengal and the calculated rate of Authors are thankful to Late Unmesh Chandra erosion in the basin is Panda without whose contribution; it would not 176.582 . The Table 6 shows have been possible to do this work. the contribution of individual metals in this respect. References Table 6 Heavy metal load with rate of erosion in the 1 Nouri J, Mahvi AH, Jahed GR, Babei AA. Regional Brahmani River basin. distribution pattern of ground water heavy metals resulting from agricultural activities. Environ. Geol. 2008; 55 (6): 1337-1343. Metal Load [ T Rate of erosion [kg 2 Singh AK, Mondal GC, Kumar S, Singh TB, Tiwary Yea ] ] BK, Sinha A. Major ion chemistry, weathering Fe 4.833 123.550 processes and water quality assessment in upper Mn 0.261 6.671 catchment of basin, India. Environ. Geo. 2008; 54 (4): 745-758. Co 0.107 2.747 3 Cravotta AC. Dissolved metals and associated Ni 0.224 5.723 constituents in abandoned coal-mine discharges, Cu 0.216 5.524 Pennsylvania, USA. Part 1: Constituent quantities and correlations. Appl. Geochem, 2008, 23 (2), 166-202. Zn 0.391 10.007 4 Venugopal T, Giridharan L, Jayaprakash M. Cr 0.762 19.480 Characterization and risk assessment studies of bed Pb 0.083 2.126 sediments of River Adyar-An application of speciation study. International Journal of Environmental 0.029 0.754 Cd Resources. 2009; 3(4): 581-598. Total load 6.907 176.582 5 Nicolau R, Galera-Cunha A, Lucas Y. Transfer of nutrients and labile metals from the continent to the Conclusion sea by a small Mediterranean river. Chemosphere. The mean concentrations of different metals in 2006; 63: 469–476. 6 Akcay H, Oguz A, Karapire C. Study of heavy metal fresh water and saline water zone follow the pollution and speciation in Buyak Menderes and order Fe> Cr> Zn> Mn> Ni> Cu> Co> Pb> Cd Gediz river sediments. Water Research. 2003; 37: and Fe> Zn> Cr> Cu> Mn> Pb> Ni> Cd> Co 813–822. respectively. The average concentration of 7 Asa SC, Rath P, Panda UC, Parhi PK, Bramha S. Application of sequential leaching, risk indices and metals in estuarine saline water zone was found multivariate statistics to evaluate heavy metal to be less than that of the river fresh water zone. contamination of estuarine sediments: Dhamara Average concentrations of all the dissolved Estuary, East Coast of India. Environ Monit Assess. metals in both river and estuary were much 2013; 185(8): 6719-6737. higher than the world river average. With 8 Sundaray SK. Application of multivariate statistical techniques in hydrogeochemical studies—A case respect to Cr and Cd the river average was above study: Brahmani–Koel River (India). Environ Monit criteria of maximum concentration (CMC) as Assess. 2010; 164: 297–310. prescribed by US Environmental Protection 9 Rath P; Bhatta D, Sahoo BN, Panda UC. Multivariate Agency, 2006. Except Fe and Mn in some statistical approach to study physiochemical characteristics in Nandira–Brahmani River. Pollution coastal stations, enrichment of all metals was Research. 2000; 19(4): 701–710. observed at all the stations. MPI values showed 10 Rath P, Panda UC, Bhatta D, Sahoo BN. that the water from stations BR_2, Br_9 and Environmental quantification of heavy metals in the BR_10 remained in class V i.e. strongly affected sediments of Brahmani and Nandira rivers Orissa, category as far as metal contamination is India. Journal of Geological Society of India. 2005; 65: 487–492. concerned. Three principal components have 11 Rath P, Panda UC, Bhatta D, Sahu KC. Use of been isolated which explained 82.99 % of the sequential leaching, mineralogy, orphology and total variance. The cross validated classification multivariate statistical technique for quantifying metal results of discriminate reveal that 88.0% of cases pollution in highly polluted aquatic sediments—a case study: Brahmani Nandira rivers, India. Journal of were classified correctly into river, estuary and Hazardous Materials. 2009; 16: 632–644. coastal groups. River Brahmani with an annual 12 Konhauser KO, Powel MA, Fyfe WS, Longstaffle FJ, discharge of 18.58 x 10 carries 6.907 x 10 Tripathy S. Trace element geochemistry of river of total heavy metals into Bay of Bengal sediment, Orissa state, India. J. Hydrology. 1997; 193: 258-268.

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