Indian Journal of Marine Sciences Vol. 38(2), June 2009, pp. 235-248 Assessment of metal concentration in the sediment cores of Manakudy estuary, south west coast of India Sugirtha P Kumar1* & J K Patterson Edward2 1 Department of Chemistry, Women’s Christian College, Nagercoil 629 001, India Suganthi Devadason Marine Research Institute, 44-Beach Road, Tuticorin 628 001, India. *[E.mail: s_prasannak@yahoo.com] 2 Received 21 November 2007; revised 21 May 2008 Base line data on the metal concentration was obtained from three core sediments (S1, S2 and S3) of Manakudy estuary on the south west coast of India. The acid leachable trace metals (Cr, Cu, Ni, Co, Pb, Zn and Cd) showed peak values at sulphidic phase . There is moderate level of pollution related to anthropogenic activities. The trace metals were associated with Fe and Mn indicating their adsorption onto Fe-Mn oxyhydroxides. The correlation of trace metals with sulphur indicates that they were precipitated as metal sulphides. Correlation matrix showed elegant association between trace metals and Fe, Mn, S and mud. The Igeo values revealed that all the core samples fell within uncontaminated to moderately contaminated category. The concentration factor was low (Cfi <1) indicating low contamination in the core samples. The anthropogenic factor (AF) values indicate moderate anthropogenic inputs. [Keywords: Trace metals, Core sediments, Contamination factor, anthropogenic factor, Igeo, Manakudy estuary, Southwest coast of India]. Introduction Estuaries are interfacial mixing zones, where river input to the ocean is modified1,2,3,4. Concentration of various elements follow closely the texture of sediments, soil particles of all sizes from clay to sand play a major role in the deposition of sediments in estuaries, particularly in semi closed or bar built estuaries5. Sediment concentrations pose one of the worst environmental problems to estuarine ecosystems. Sediments may not only act as sinks but also as sources of contaminants in aquatic systems6,7. Contaminants, including trace metals can be introduced into the aquatic environment and accumulate in sediments by several pathways including disposal of liquid effluents, runoff and leachates carrying chemicals originating from a variety of urban, industrial and agricultural activities as well as atmospheric deposition. Heavy metals are critical in pollution of ecosystem because of their easy uptake into the food chain and also because of bioaccumulation processes8. Estuarine sediments may serve as effective traps of river borne metals9 The concentration of metals found in recent sediments are significantly higher when compared to sediments that are deposited during pre-industrial time10. Most trace metal contaminants are, however, adsorbed to or occluded within the hydrogenous and biogenic phases, which coat natural particles11,12,13. Metals accumulated in this way may be subsequently released to the overlying water column as a result of either physical disturbance or diagenesis and the sediments may persist as a source of pollutants long after the cessation of direct discharges. Diagenetic reactions are important near the sediment – water interface responding to redox changes and affecting metal concentrations in vertical sediment profiles14. The assessment of trace metal pollution in sediments, analysis of the non-residual fractions (acid leachable) is of prime importance. The sediment act as a useful indicator of long and medium term metal flux in industrialized estuaries and rivers, and they help to improve management strategies as well as to assess the success of recent pollution controls15,16,17. Acid leachable trace metals are not part of the silicate matrix and have been incorporated into the sediment from aqueous solution by processes such as adsorption and organic complexation. The study of core samples provides historical record of various influences on the aquatic system by indicating both the natural background levels and the man-induced accumulation of trace metals over an extended period of time. 236 INDIAN J. MAR. SCI., VOL. 38, NO. 2, JUNE 2009 The environmental chemistry of river basin and small estuaries in India has received less attention, despite some environmental studies in major rivers18,19. The present study is an attempt to delineate core sediments of Manakudy estuary and to assess level of trace metal concentration due to industrial, agricultural and domestic effluents in three stations (S1, S2 and S3) of the Manakudy estuary situated on the southwest coast of India. Materials and Methods Study Area The Manakudy estuary is the confluence of river Pazhayar and has an area of about 150 ha (Fig. 1). It is a sand built estuary connected to the sea during the rainy season. During the period of total occlusion of the river mouth the estuarine water swells due to heavy inflow of water from the head of the estuary and also by the land drainage. During heavy inflow into the estuary the sand bar opens up under the force of gravity. Manakudy estuary abounds with fishery resources and has neighbouring fishing helmets. There are no major industries near the estuary, however three small-scale industries viz coconut husk retting, lime shell dredging and salt works are well established on the banks of the estuary. Further there is heavy surface runoff from the paddy fields and coconut plantations into the estuary. Fig. 1—Location of the stations in the Manakudy Estuary Sample collections Sediment core samples were collected at three stations (S1, S2 and S3) along the course of the estuary. The station I (Core1) was selected at the mouth of the estuary, station II (Core 2) was selected near the mangroves and the station III (Core 3) was selected near the head of the estuary. A PVC coring tube (7.5 cm diameter and 2.5 m length), precleaned with acid was used for the collection of core samples. The PVC tube was driven into the sediment until about 50 cm of the pipe remained above the ground and the rest was filled with ambient water on the top. The PVC tube was sealed using a plumber’s dummy and it was sealed and pulled out from the sediment. The water on the top was then decanted and the pipe was just cut off above the top of the cored sediment and the plastic bags were taped over both ends of the PVC tube20. From the core samples S1 (Core1) S2 (Core 2) and S3 (Core 3) 26, 24 and 25 sub samples were made respectively by cutting the coring tube at 2.5 cm interval. The geochemical data presented in this study have not been corrected for compaction, as it is likely to be uniform down the length of the core21. Textural studies for sand, silt and clay were performed22 and the Calcium carbonate23 and organic carbon24 content were determined. Na+ and K+ concentrations were determined with a flame photometer using suitable chemical standards. Ca2+ and Mg2+ were determined using standard methods25. For acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) 5 g of dry sediment sample was taken in a 100 ml plastic bottle in which 75 ml of 0.5 N HCl was added and after mechanically shaking for 16 hr it was filtered with Whatman Grade A filter paper26,27. The filtered samples were measured in flame ASS (Varian Spectr AA 200 AAS) equipped with a deuterium background corrector for analysis of acid leachable trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb and Zn). A graphite furnace was used for the determination of Cd due to its low concentration.. Standard reference material BCSS-1 was used to ensure the quality control and accuracy of the analysis. Analysis of triplicates for every fifth sample suggest that the precision of analysis lie in the following coefficient of variation Fe 2.6%, Mn 1.8%, Cr 3.7%, Cu 2.4%, Ni 2.6%, Co 2.2%, Pb 2.5%, Zn 3.7% and Cd 3.9%. Statistical analyses based on acid leachable elements were effectively utilized for the interpretation of geochemical processes20,28,29,30,31,32 KUMAR & EDWARD: METAL CONCENTRATION IN THE SEDIMENT CORES OF MANAKUDY Index of Geoaccumulation The Index of Geoaccumulation computed using the equation32,33. (Igeo) was Igeo = log2 Cn / 1.5 Bn Where Cn is the measured concentration of the element in the politic sediment fraction and Bn is the geochemical background value (average shale) in the earth’s crust34. The constant 1.5 allows for natural fluctuations in the content of a given substance in the environment and very small anthropogenic influences32. Six classes of the geochemical index35 has been distinguished Class 0 Value Igeo<0 1 0< Igeo<1 2 3 4 5 6 1< Igeo<2 2< Igeo<3 3< Igeo<4 4< Igeo<5 5< Igeo Soil quality Practically uncontaminated Uncontaminated to moderately contaminated Moderately contaminated Moderately to heavily contaminated Heavily contaminated Heavily to extremely contaminated Extremely contaminated Enrichment Factor The enrichment factor (EF) was based on the standardization of a tested element against a reference. A reference element is the one characterized by low occurrence variability. The most common reference elements are Sc, Mn, Ti, Al and Fe36,37,38,39,40. In the present study Fe was used as the reference metal using the formula41. 237 Anthropogenic factor The enrichment is normalized relative to the depth in the sediment core using the following formula AF = Cs/Cd where Cs and Cd refer to the concentration of the elements in the surface sediments and at depth in sediment column42. If AF is > 1 for a particular metal, it means, contamination exists; otherwise if AF ≤ 1, there is no metal enrichment of anthropogenic origin43. Contamination factor The assessment of soil contamination was also carried out using the contamination factor 44. C if = C oi − 1 C ni Where C 0i − 1 is the mean content of metals from at least five sampling sites and C ni is the concentration of elements in Earth’s crust as a reference value. Pollution Load Index (PLI) The pollution level in trace metal was calculated by the method based on pollution load index 45. CF = C metal / C background PLI = n (CFI × CF2 × CF3 × ......CFn) CF = Contamination factor n = number of metals Cn (sample)/Cref (Sample) EF= Bn (background)/Bref (background) Where Cn (sample) is the content of the examined element in the examined environment. Cref (sample) is the content of the reference element in the examined environment. Bn (background) is the content of the examined elements in the reference environment and Bref (back ground) is the content of the reference element in the reference environment. Five contamination categories are recognized on the basis of the enrichment factor40. EF<2 EF=2-5 EF=5-20 EF=20-40 EF>40 Deficiency to minimal enrichment Moderate enrichment Significant enrichment Very high enrichment Extremely high enrichment C metal = metal contamination in polluted sediment. C back ground value = back ground value of that metal. Four categories of contamination factor have been distinguished44. Cfi <1 1≤Cfi <3 3≤Cfi < 6 6≤Cfi Low contamination factor indicating low contamination Moderate contamination factor Considerable contamination factor Very high contamination factor Results and Discussion Sediment Texture Textural studies in the three core samples (S1, S2 and S3) showed that the percentage of sand and mud INDIAN J. MAR. SCI., VOL. 38, NO. 2, JUNE 2009 238 (silt + clay) differed markedly in relation to depth. Studies reveal two distinct characters, the upstream side (S2 and S3) was characterized by (71.98% and 79.81%) sand and the downstream estuarine side (S1) was dominated by mud (Silt + Clay). The higher mud content in the downstream estuarine station (S1) is due to the low fluvial discharge and a better mixing of saline and fresh water that facilitated flocculation and faster settling of suspended particles46. The higher sand content (> 90%) at 35-50 cm depth in S2 and 42.5-60 cm depth in S3 indicating a relatively higher energy regime that prevents sedimentation of fine-grained particles20. In addition, S3 shows a good variation in sand content from 27.5-60 cm indicating the low flow condition, where finer particles have settled down in the upstream side and it is similar to other Southeast Coast rivers20,47. Similar observations were made in the river Uppanar on the southeast coast of India20 (Table 1). Calcium carbonate, organic carbon and Sulphur Vertical distribution of CaCO3 in all the three core samples indicates average values of 16.59%, 4.45% Table 1—Sand and Mud contents in the core samples from Manakudy estuary Depth Sand% Mud%(Silt+Clay) (cm) S1 S2 S3 S1 S2 S3 2.5 5 7.5 10 12.5 15 17.5 20 22.5 25 27.5 30 32.5 35 37.5 40 42.5 45 47.5 50 52.5 55 57.5 60 62.5 65 64.94 38.92 29.31 28.17 34.53 49.02 20.38 18.05 26.57 18.54 20.85 34.6 46.22 35.24 53.08 43.88 34.6 47.58 50.66 61.94 56.71 58.93 57.58 61.06 48.69 48.67 33.79 37.71 49.17 67.9 70.25 75.14 76.99 83.14 74.56 67.61 52.73 52.55 77.89 91.35 91.72 89.03 90.85 94.88 95.86 96.44 74.55 40.05 86.52 57.01 66.23 78.18 84.5 52.27 72.69 63.57 62.82 68.76 74.08 72.28 86.57 87.09 86.02 88.76 87.29 85.04 90.13 89.3 89.95 89.58 89.66 92.24 93.32 88.84 56.08 35.06 61.08 70.69 71.83 65.47 50.97 79.61 81.96 73.43 81.46 79.15 65.39 53.78 64.76 46.92 56.12 65.4 52.42 49.34 38.07 43.29 41.08 42.42 38.95 51.3 51.33 66.21 62.29 50.83 32.1 29.76 24.86 23.01 16.85 25.44 32.73 47.27 47.45 22.11 8.65 8.28 10.97 9.15 5.12 4.14 3.56 25.45 59.95 13.48 42.99 33.77 21.82 15.5 47.732 27.31 36.43 37.18 31.24 25.92 27.72 13.429 12.91 13.98 11.24 12.71 14.96 9.87 10.7 10.05 10.42 10.34 7.76 6.68 11.16 43.92 and 13.84% in S1, S2 and S3 respectively (Fig. 1). Peak values of CaCO3 at surface level in S1 and S3 are due to the shell fragments present in the sediments. Further the CaCO3 profiles indicate enrichment at deeper layers (45-65 cm in S1 and 30-57.5 cm in S3) and it may by enrichment of the reduced layers due to reprecipitation and increase in alkalinity generated by sulphate reduction48. Overall, CaCO3 distribution indicates low values at the midstream side (S2). The present trend is in agreement with the similar observations made in the Uppanar river on the Southeast coast of India20. Organic carbon (OC) content indicates variation in all the stations (Fig. 2). Enrichment of OC at different core intervals indicates incorporation of organic materials from the river water matter. The enrichment of OC in subsurface and deeper layers suggests deposition under calm conditions prevailed during the slow accumulation of finer sediments49. Further organic carbon increases with increasing finer fraction and decreases with the increasing coarser fraction in the sediments. One of the features of organic carbon in the sediments is that its concentration increases as the particle size of the sediments decrease50. The finer fractions (Silt + Clay) showed an efficacious relationship with organic carbon while the coarser fractions have no patent kinship. The relatively lower percentage of organic carbon in the top layers (0-2.5 cm) than the subsurface in S1 could be attributed to the constant flushing activity by tides along with the impact of waves which removes the finer fractions of the sediments from the fringing area. The tidal influence and wave action are maximum at S1 since it is near to the bar mouth area. Also the organic residues from the decomposed matter appear to be subsided more in the surface by percolation process50. Sulphur The down core profiles of total sulphur (S) in S1, S2 and S3 indicate a gradual increase of S from fresh water zone to the estuarine region (Table 2. Fig. 2). The concentration of S in surface layers in all core samples indicates that it is transported from bottom sediment layers to the sediment-water interface51. The oxidation of Fe-sulphides is responsible for the decrease in S content at the middle zone of the core samples S1 and S3. There is enrichment of sulphur below the suboxic / anoxic interface indicating that sufficient oxidants must be present to generate sulphides at these depths KUMAR & EDWARD: METAL CONCENTRATION IN THE SEDIMENT CORES OF MANAKUDY 239 Fig. 2—Vertical profiles of CaCO3, Organic Carbon and S in the core sediments Table 2—Average values for all geochemical parameters analysed in core samples (S1, S2 and S3) collected from Manakudy estuary Elements S1 S2 S3 CaCO3 (%) OC (%) S (%) Fe (µgg-1) Mn (µgg-1) Cr (µgg-1) Cu (µgg-1) Pb (µgg-1) Zn (µgg-1) Co (µgg-1) Ni (µgg-1) Cd (µgg-1) Na (µgg-1) K (µgg-1) Ca (µgg-1) Mg (µgg-1) 16.596 1.294 0.863 4887.462 358.216 482.138 43.677 176.877 72.623 4.004 28.912 2.819 10476.923 8106.038 3882.154 5284.064 4.458 0.875 0.760 4737.792 236.238 377.454 45.867 161.254 71.946 4.400 24.275 2.696 9791.667 9633.250 2448.458 5126.326 13.846 0.839 0.570 4561.462 166.988 256.908 37.352 152.248 54.584 6.052 20.148 3.168 10768.000 9974.000 1673.560 5248.435 and they are metal oxides, which interact with sulphur species to form sulphides52. The complete oxidation of sulphides with Fe3+has been documented at low pH in non-marine environment53,20. However, these results reveal that the flux of liable organic matter to the sediments is very low, resulting in low values after sulphate reduction. Overall sulphur results indicate complete oxidation of H2S all along the riverine sediments resulting in low values in the study area20,54. The significant relationship of S with trace metals shows that these trace metals are precipitated as metal sulphides and are also responsible for the fixation of trace metals in core sediments55. Down core profiles of acid leachable elements Fe and Mn The vertical profiles of S1 and S3 show enrichment in the surface layers due to early diagenetic process. A decrease in Fe and Mn at the subsurface is suggestive of the oxic / suboxic interface14. The Fe–Mn oxyhydroxides dissolved in partly reduced 240 INDIAN J. MAR. SCI., VOL. 38, NO. 2, JUNE 2009 sediment migrate upward in the sediment column and get precipitated. But in S2, there was increase in concentration of Fe and Mn at deeper layers which indicates a reduced layer well above the other core samples (S1 and S3) Fig. 3a, b & c. Enrichment of Fe and Mn in HCl extractable fraction near the interface in all the core samples indicates that recycling is more intensive under low oxygen conditions. Further, diagenetic enrichment of Fe starts at greater depth compared to Mn indicating higher stability of Fe-Mn oxyhydroxides under reducing conditions and faster oxidation kinetics of Fe2+ compared to Mn2+ and is precipitated as metalliferrous sulphides formed under anoxic conditions56. The internal recycling of Mn in sediments either leads to the formation of a Mn peak near the sediment redox boundary or to surficial Mn-rich oxic sediments. In addition Mn is enriched in the surface layers of all the core samples indicating that Mn2+ has diffused into the suboxic zone and has precipitated as Mn oxides and subsequently was reduced again upon downward transport20. The formation of Mn peak occurs when pore water Mn concentrations are low in the suboxic zone and the redox boundary is relatively deep as in S1 and S3 due to low organic carbon (OC) flux in the sediments57. Overall Fe and Mn enrichment in S1 than other core samples indicates recycling of Fe and the resuspension of bottom sediments is due to tidal mixing from the coastal zone20,58. In addition, estuarine mouth acts as an ultimate sink for most liable Mn entering the estuarine region (S1), where the depth is also very low20,59. Cr, Cu, Ni, Co, Pb, Zn and Cd The trace metal concentrations (Cr, Cu, Ni, Co, Pb, Zn and Cd) have a similarity among them at different depths and indicate that the main source of input to the Manakudy estuary is from the upstream side. Metal peaks along reduced layers are clearly observed in S1 and S3 (Fig. 3). The metal peaks also indicate scavenging of trace metals by Fe and Mn Fig. 3(a)—Vertical profiles of metals in the core sediments S1, S2 and S3 KUMAR & EDWARD: METAL CONCENTRATION IN THE SEDIMENT CORES OF MANAKUDY Fig. 3(b)—Vertical profiles of metals in the core sediments S1, S2 and S3 241 242 INDIAN J. MAR. SCI., VOL. 38, NO. 2, JUNE 2009 Fig. 3(c)—Vertical profiles of metals in the core sediments S1, S2 and S3 KUMAR & EDWARD: METAL CONCENTRATION IN THE SEDIMENT CORES OF MANAKUDY oxyhydroxides and are deposited as metal sulphides with a common source of origin for S1 and S360. Cr concentration in the top layers in S2 and S3 indicate that it is present as Cr (VI), which is relatively mobile and after release to the pore waters, they migrate downward into the reducing zone and precipitates again as Cr(OH)261. The hydrolysed form of Cr (VI) are readily adsorbed by hydrous Fe and Mn oxides62. Down core profiles of Cu, Ni and Co indicate moderate removal in the suboxic layers till the zone of oxygen penetration. Distribution pattern of Ni and Co are similar to those of Fe and Mn indicating that they are cycled along with Fe-Mn oxides in the redox boundaries and are precipitated as iron sulphides63. In addition the results suggest that the increase of Ni and Co in S1 and S3 is specially linked to the anoxic conditions and the addition of these elements is due to the scavenging of Fe-Mn oxides20. Profiles of Pb in the surface layers show higher concentration in S3 than in S2 and S1 and are attributed to the local redox conditions, which allowed Pb to co-precipitate with Mn during Mn oxide formation in the superficial segment. Additional Pb has reprecipitated along the redox boundaries and the downward flux is also bound to biogenic particles64. The average values of Zn are high in S1 and S2 compared to S3. Zn can enter the aquatic environment from a number of sources including sewage effluent and runoff65. Input of organic wastes into the estuary, which comes from sewage, contributes to the Zn increase in sediments66. Cd indicates that dissolution is taking place in the upper most layers of S2 with very low values. The dissolution of Cd is oxygen dependent in the aerobic degradation of the fresh organic matter to which Cd is initially bound, followed by the migration of the water column and downward into the sediment with high peaks in deeper layers. The results indicate that acid leachable trace metals (Cr, Cu, Ni, Co, Pb, Zn and Cd) demonstrate moderate level of pollution related to anthropogenic activities20. The coincident peaks more or less at the same depth displayed by trace metals suggest the contribution of post-deposited effects, such as reduction of sulphides and formation of metallic ferrous sulphides, under anoxic conditions or reprecipitation of trace metals on Fe/Mn oxides and oxyhydroxides coatings67,68. The low OC content 243 causes the redox cycling of the metals to occur relatively deep in the core sediments and the efficient trapping of the ions within the sediment results in a build-up of the oxide concentrations at the suboxic/anoxic boundary69 (Fig. 3 & Table 2). Elemental Concentration in the Core samples The enrichment of metals was assessed in relation to sequence (ES) and anthropogenic factor (AF) (Table 3). The elemental sequence42 in the core samples are placed in the following order S1=Na > K > Fe > Mg > Ca > Cr > Mn > Pb > Zn > Cu > Ni > Co > Cd. S2= Na > K > Fe > Ca > Mg > Cr > Mn > Pb > Zn > Cu > Ni > Co> Cd. S3= Na > K > Fe > Ca > Mg >Cr > Mn > Pb > Zn > Cu > Ni > Co > Cd. The anthropogenic factor (AF) was assessed43 and the metals are enriched as follows S1= Co> Ca > Cd > Ni > Mg> Na > Cu > K > Zn >Fe > Cr > Mn > Pb S2= Mg > Ca > Mn > Ni > Co > Zn > Cu >Na > Cr > K > Fe > Pb > Cd. S3= Mg >Ca > Zn > Na > Cd > Co > K > Cu > Pb > Fe > Ni > Mn > Cr. The calculated AF values indicate that 70% of the metals in the core samples are moderately enriched, suggesting anthropogenic input of industries and sewage load along the river bank70,71. The effluents from the coir retting pits and domestic sewage from the fishermen settlements are the chief sources of Table 3—Average values of anthropogenic factor (AF) in core samples (S1, S2 and S3) from Manakudy Estuary Elements S1 S2 S3 Fe Mn Cr Cu Pb Zn Co Ni Cd Na K Ca Mg 0.979 0.761 0.965 1.452 0.723 1.006 2.858 1.543 2.358 1.491 1.211 2.518 1.534 1.054 1.793 1.340 1.425 0.784 1.542 1.566 1.601 0.486 1.403 1.186 2.189 3.466 0.980 0.661 0.521 1.316 1.263 1.933 1.423 0.732 1.521 1.772 1.361 1.951 2.837 244 INDIAN J. MAR. SCI., VOL. 38, NO. 2, JUNE 2009 Fig. 4(a-c)—Enrichment factor in station 1; Enrichment factor in station 2; Enrichment factor in station 3 KUMAR & EDWARD: METAL CONCENTRATION IN THE SEDIMENT CORES OF MANAKUDY 245 Fig. 5(a-c)—Index of Geoaccumulation in station 1; Index of Geoaccumulation in station 2; Index of Geoaccumulation in station 3 246 INDIAN J. MAR. SCI., VOL. 38, NO. 2, JUNE 2009 pollutants to the estuary. Though there are no industries around the estuary the river Pazhayar drains pollutants from industries situated in nearby towns which include dyeing units. The fertilizers in the agricultural waste water drained from the paddy fields are the main source of heavy metals. The enrichment factor (EF) is based on the standardization of the tested element against iron. It was found that only Na and K have values between 2 and 5 (EF=2 - 5) showing moderate enrichment. All other elements have EF <2 showing no enrichment (Fig. 4(a-c)). Index of Geoaccumulation (Igeo) Possible sediment enrichment of metals in Manakudy was evaluated in terms of the Igeo values72. The obtained Igeo values revealed that all the core samples fell within uncontamination to moderately contaminated category (Fig. 5(a-c)). Similar observations were made in the soils of Suszee commune, Poland32 in which there was enrichment in Cd, Pb, As and Hg and there was elevated Igeo values for Fe and Mn in the surface of Mandovi estuary, west coast of India, during the premonsoon period66. The contamination factor44 was calculated for the core samples S1, S2 and S3. The contamination factor was low (Cfi <1) indicating low contamination in the core samples of Manakudy estuary. Inter-element relationship The results of correlation matrix of each core sample indicate that a significant fraction of the trace metal are found co-precipitated with or adsorbed on to Fe and Mn geochemical phases controlling the trace metals in sediments. These characters are due to their large surface area, extensive cation exchange capacity and widespread availability42. The strong correlation of trace metals with mud (Silt + Clay) indicates that they are concentrated to the fine-grained particles and are hosted by clay phases. There was positive correlation between metals and organic carbon. The correlation matrix showed that Fe has significant positive correlation with Cr, Cu and Mg (P <0.05); Mn has significant positive correlation with Ni, Cr, Zn, Na, K and Mg (P <0.01); Cu has significant positive correlation with Zn, Ca, Fe and Cr (P <0.05) and Zn has significant positive correlation with Fe, Mn, Cr, Cu, Ni, Na, K and Mg (P <0.01). The acid leachable trace metals (Cr, Cu, Ni, Co, Pb, Zn and Cd) demonstrate moderate level of pollution related to anthropogenic activities (Table 3). The Igeo reveals that the sediments are uncontaminated. The contamination factor is also low in the sediments. The level of metal pollution in Manakudy estuary is low and it is due to the absence of major factories in and around the estuary. The only pollution load is from the coir retting pits and sewage from the fisherman settlements. Further there is surface runoff that bring in inorganic fertilizers into the estuary. 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