The results of the percentage compositions of sand, silt and clay of the selected sediment samples from Ennore and Tuticorin coasts are given in Fig. 2.The percentage of sand fraction at Ennore coast was found to have varied from 12.79 to 85.16% with a mean value of 36.28% ± 8.68%. The maximum percentage of sand (85.16%) was noticed at Ennore creek mouth (ENN-III) during the post monsoon season. The minimum of 12.79% was measured during the pre-monsoon season in the Ennore creek region (ENN-I). The percentage of silt fraction was found to have varied from 10.57 to 59.47%with a mean value of 39.98% ± 4.96%.The higher percentage of silt (59.47%) was noticed in sample from Ennore creek (ENN-II) during the monsoon season. The lower percentage of silt (10.57%) was observed during the post monsoon season in the sample from Ennore creek mouth (ENN-III) and the percentageof clay fraction was found to have varied from 2.27 to 52.62% with a mean value of 23.74% ± 4.42%. The maximum percentage of clay fraction (52.62%) was observed during the monsoon season in the Ennore creek sample (ENN-I) and the lower percentage of 2.27% was observed during the summer season in the Ennore creek mouth sample (ENN-III). In Tuticorin samples,the sand fraction was found to have varied from 13.42 to 84.16% with a mean value of 42.20% ± 2.65%. The maximum percentage of sand (84.16%) was noticed at Tuticorin channel mouth (TUT-III) during the summer season whereas minimum of 13.42% was measured during the post monsoon season in the Korampallam channel (TUT-I). The percentage of silt fraction was found to have varied from 12.07 to 46.14% with a mean value of 32.90% ± 1.55%. The higher percentage of silt (46.14%) was noticed during the monsoon season in the Korampallam channel (TUT-I) whereas lower percentage (12.07%) was observed during the post monsoon season in the Tuticorin mouth region (TUT-III). The percentage of clay fraction was found to have varied from 3.57 to 45.63% with a mean value of 24.89% ± 1.50%.The higher percentage of clay (45.63%) was observed during the monsoon season (TUT-VI) whereas lower percentage (3.57%) was observed during the summer season in the sample from Tuticorin channel mouth (TUT-III).
In general, the average percentage of silt fraction was calculated and found higher when compared with other fractions and it further indicates that the Ennore creek and Tuticorin channel receive higher fractions of silt because of the continuous disposal of sewage into these water ways. When considering the seasonal fluctuation, higher percentage of sand fractions was observed during the monsoon season which led to heavy flooding in the rivers which further erodes the land and makes influx of sand considerably higher, as reported by Veerasingam et al., (2010) and Almeida et al., (2018).
There were reports on sediment compositions available previously in the studied coastal region under present study by Joydas and Damodaran (2009) and Yuan et al., (2017). Particularly, in the continental shelf region of southeast coast of India and west coast of India, respectively. The results of present study have good agreement with before mentioned studies as the sediment composition dominated with higher percentage of sand followed by silt and clay during the monsoon season.
The seasonal and spatial variations in the levels of TOC are presented in Table 1. The total organic carbon was found to have varied from 1.55 to 12.58mgC g− 1 with a mean value of 5.38 ± 0.51mgC g− 1, in the samples from Ennore region. The highest TOC was observed (12.58 mgC g− 1) during the post monsoon season in 2014 in sample from station ENN-I of Ennore creek. The lower value of TOC (1.55 mgC g− 1) was found during the summer season in 2013 in sample from station ENN-III of Ennore coast. In the samples from Tuticorin region, the TOC was found to have ranged from 1.49 to 7.13mgC g− 1with a mean value of 4.04 ± 0.27mgC g− 1. The higher value of TOC (7.13 mg g− 1) was observed during the post monsoon season in 2014 in sample from station TUT-I whereas, the lower value of TOC (1.49 mg g− 1) was found during the summer season in 2013 in sample from station TUT-III. This clearly shows that the TOC level is high in Ennore study area when compared to Tutcorin study area. The increased value of TOC in monsoon season might be due to the higher sedimentation process which is taking place in every monsoon season in addition to the continuous discharge of sewage and industrial wastes into the Ennore creek (ENN-I). Total organic carbon (TOC) and clay shows similar patterns of distribution in both study areas and a positive correlation (r = 0.894, p = 0.01 and r = 0.925, p = 0.01) is found which is presented in Table 2.
Table 1
Spatial and seasonal Variation of TOC from Ennore and Tuticorin harbour sediments.
|
SUM '13
|
PRM'13
|
MON'13
|
POM'14
|
ENN-I
|
10.24 ± 0.07
|
10.85 ± 0.06
|
12.47 ± 0.04
|
12.58 ± 0.13
|
ENN-II
|
5.61 ± 0.05
|
5.85 ± 0.03
|
6.42 ± 0.10
|
6.35 ± 0.06
|
ENN-III
|
1.55 ± 0.08
|
1.66 ± 0.02
|
2.04 ± 0.03
|
2.43 ± 0.06
|
ENN-IV
|
2.11 ± 0.07
|
2.39 ± 0.03
|
2.64 ± 0.05
|
2.20 ± 0.07
|
ENN-V
|
4.14 ± 0.06
|
4.26 ± 0.07
|
5.32 ± 0.15
|
5.05 ± 0.13
|
ENN-VI
|
5.25 ± 0.10
|
5.69 ± 0.03
|
6.07 ± 0.20
|
6.36 ± 0.08
|
TUT-I
|
6.23 ± 0.09
|
6.63 ± 0.05
|
6.99 ± 0.17
|
7.13 ± 0.04
|
TUT-II
|
4.13 ± 0.24
|
4.73 ± 0.13
|
5.19 ± 0.19
|
5.45 ± 0.25
|
TUT-III
|
1.49 ± 0.02
|
1.56 ± 0.05
|
2.12 ± 0.20
|
1.72 ± 0.06
|
TUT-IV
|
2.16 ± 0.026
|
2.72 ± 0.04
|
2.89 ± 0.04
|
1.70 ± 0.13
|
TUT-V
|
3.28 ± 0.07
|
3.50 ± 0.08
|
3.98 ± 0.24
|
4.27 ± 0.23
|
TUT-VI
|
5.00 ± 0.45
|
4.78 ± 0.08
|
5.60 ± 0.23
|
5.11 ± 0.04
|
Table 2
Spatial and seasonal variation of TPH from Ennore and Tuticorin harbour sediments.
|
SUM '13
|
PRM'13
|
MON'13
|
POM'14
|
ENN-I
|
14.68 ± 0.35
|
13.82 ± 0.09
|
15.70 ± 0.21
|
17.47 ± 0.06
|
ENN-II
|
8.48 ± 0.05
|
7.30 ± 0.12
|
9.40 ± 0.06
|
10.51 ± 0.20
|
ENN-III
|
3.45 ± 0.03
|
3.25 ± 0.07
|
3.74 ± 0.13
|
4.18 ± 0.10
|
ENN-IV
|
10.49 ± 0.05
|
9.75 ± 0.09
|
12.62 ± 0.11
|
14.28 ± 0.12
|
ENN-V
|
9.67 ± 0.08
|
8.68 ± 0.19
|
9.45 ± 0.20
|
10.34 ± 0.14
|
ENN-VI
|
8.41 ± 0.12
|
8.38 ± 0.22
|
8.69 ± 0.09
|
9.25 ± 0.11
|
TUT-I
|
9.48 ± 0.11
|
9.68 ± 0.16
|
9.73 ± 0.19
|
10.16 ± 0.14
|
TUT-II
|
7.20 ± 0.013
|
6.39 ± 0.20
|
7.00 ± 0.16
|
7.34 ± 0.05
|
TUT-III
|
2.20 ± 0.13
|
2.05 ± 0.09
|
2.18 ± 0.15
|
2.43 ± 0.23
|
TUT-IV
|
4.75 ± 0.21
|
4.20 ± 0.14
|
4.89 ± 0.32
|
5.57 ± 0.27
|
TUT-V
|
6.35 ± 0.16
|
6.75 ± 0.32
|
6.18 ± 0.10
|
7.32 ± 0.14
|
TUT-VI
|
7.82 ± 0.14
|
7.65 ± 0.18
|
8.47 ± 12
|
8.09 ± 0.03
|
The results also indicate that the gradual deposition of organic matter observed in present study is may become less significant in course of time, and it might be due to lesser deposition of clay from the river and sewage which in turn does not support to retain TOC. In contrast to the present study, the study made by Hong-Gung Ni et al., (2008) reported high amount of TOC in their study area in spite of having high amount of sand portion. Considering the average values of TOC in the two study areas under our present study, Ennore creek and its coastal areas were found to have higher average values of TOC as compared to Tuticorin study area. This might be due to the higher deposition of the sewage and industrial wastes in the Ennore creek area as compared to Tuticorin. The significant relationship between TOC and clay was reported by Kim et al., (2017) Yan et al., (2019) showed a linear positive relationship between TOC and clay,similar to the results observed in the present study. Recent studies by Hassan et al., (2018) established that this relationship is significant. Generally, fine fractions prevent the diffusion of oxygen into sediments, thus allowing for the conservation of organic matter, which in turn helps the enhancement of total organic carbon (TOC) concentrations in the sediments.
The observed values of TPH in both study areas are presented in Table 2.The total petroleum hydrocarban at Ennore region was found to have varied from 3.25 to 17.47 µg g− 1with a mean level of 9.63 ± 1.05µg g− 1. The higher level of TPH was observed (17.47 µg g− 1) during the post monsoon season, 2014 from samples of station ENN-I of Ennore creek whereas, the lower value of TPH (13.25 µg g− 1) was found during the pre-monsoon season, 2013 from samples of Ennore channel mouth (ENN-III). The total petroleum hydrocarban (TPH) at Tuticorin was found to have ranged from 2.05to 10.16 µg g− 1with a mean value of 6.41 ± 0.25µg g− 1.The maximum level of TPH was observed (10.16 µg g− 1) during the post-monsoon season, 2014 in samples from station TUT-I while the minimum level of TPH (2.05 µg g− 1) was found during the pre-monsoon season, 2013 in samples from Tuticorin channel mouth (TUT-III).
The higher TPH load recorded in Ennore creek region (ENN-I) might be due to the frequent discharges from nearby petro chemical industries. In the present study, the maximum concentration of TPH was observed during the monsoon season, which clearly indicates that the flood during the northeast monsoonal rainfall transports the higher quantity of TPH to these coastal areas. Similar to the present study Venkatachalapathy et al., (2015), reported higher values of TPH concentration in sediments (1.88–39.76 ppm) from Chennai coast, Southeast coast of India. The TPH concentrations showed extensive fluctuations because of the differential rate of input through river transport in different seasons. Therefore, a distinct seasonal variation could be observed in the levels of TPH in samples from different study areas. The reason for petroleum hydrocarbon values recorded to be lower in ENN-III (Ennore creek mouth) & TUT-III (Tuticorin channel mouth), might be attributed to high proportion of sand which has less efficiency in binding the TPH whereas higher levelsof TPH in the Ennore creek and Tuticorin channel (ENN-I & TUT-I) could be noticed due to high proportions of silt and clay.
Similarly, Veerasingam et al., (2010); Muthukumar et al., (2013) reported 4.23ppm of TPH at Narimanam and 1.48 ppm of TPH at Nagapatinnam coasts of Tamil Nadu. Sediments containing fine particles are always found to be good accumulators of organic pollutants presumably because of their greater affinity towards pollutants like TPH (Law and Klungsoyr, 2000). The fine sediment fractions like clay which are dispersed in the water column have high absorbing characters and they effectively scavenge the trace contaminants that enter the aquatic ecosystem (Wang et al., 2014).
Pearson's correlation coefficient was applied for both the study areas to understand the relationships among TPH, TOC and soil characteristic sand the results are presented in Tables 3 and 4. A positive correlation was found between TPH and soil fractions such as clay and silt but the sand showed negative correlation.The significant correlations between TPH with TOC, clay and silt suggest that the TPH is strongly bound with TOC in clay and silt enriched sediments.
Table 3
Correlation matrix in Ennore stations.
|
TOC
|
TPH
|
Sand
|
Silt
|
Clay
|
TOC
|
1
|
|
|
|
|
TPH
|
.723*
|
1
|
|
|
|
Sand
|
− .931**
|
− .764
|
1
|
|
|
Silt
|
− .177
|
− .419
|
− .017
|
1
|
|
Clay
|
.894*
|
.877*
|
− .852*
|
− .509
|
1
|
**. Correlation is significant at the 0.01 level (2-tailed). |
*. Correlation is significant at the 0.05 level (2-tailed). |
Table 4
Correlation matrix in Tuticorin stations
|
TOC
|
TPH
|
Sand
|
Silt
|
Clay
|
TOC
|
1
|
|
|
|
|
TPH
|
.965**
|
1
|
|
|
|
Sand
|
− .918**
|
− .980**
|
1
|
|
|
Silt
|
.855*
|
.948**
|
− .966**
|
1
|
|
Clay
|
.925**
|
.962**
|
− .983**
|
.901*
|
1
|
**. Correlation is significant at the 0.01 level (2-tailed). |
*. Correlation is significant at the 0.05 level (2-tailed). |
The values of TOC and TPH are depicted in Fig. 5. The variation of TOC, clay and TPH of Ennore station was noticed to have positive correlation between TOC, clay, silt and TPH. In the present study, temporal variations of TOC and TPH values were found with highly positive correlation and are shown in Tables 2 and 3. This indicates that the input of TPH to the study area was related to TOC levels.
As in the case of present study, Zhang et al., (2006), and Adeniji et al., (2017) reported that the TOC has positive relationship with hydrocarbons in the sediments from China, Hong Kong and South Africa respectively. In addition, it was confirmed that the hydrocarbons’ levels in the sediments from Ennore and Tuticorin areas were higher and the TOC levels were found to be elevated in the sample sediments (R2 = 0.723, P < 0.05 and R2 = 0.965 P < 0.01) Tables 3 and 4. Warren et al., (2003) suggested that sorption of hydrocarbons takes place directly on sediment surfaces when the organic matter deposition is significant. The studies by different researchers (Ruiz-Fernández et al., 2012; Vagge et al., 2018) also support the fact that the silt and clay have significant affinity to TOC and hydrocarbons. The accumulation of hydrocarbons is mainly influenced by the factors such as the type of hydrocarbons and its sources (pyrolytic and / or petrogenic) and most significantly the type of sediment (rated by the presence of organic matter) which receives the TPH (Wang et al., 2014). The high presence of sand fractions in the sediment samples (60–99%) would have no impact on PAHs retention in the sediments. There were conflicting reports (Le Boeuf and Weber, 1997) which proposed that organic particles in sediments containing majority of clay and silt fractions are more likely to be despoiled than those of thicker grained sediments like sand, which is considered to be the most effective factor that influences the sorption characteristics of hydrocarbons.
The level of petroleum hydrocarbon concentrations in the present study are comparable with those reported from coastal and estuarine regions of various countries, Arabian sea along the Indian coast (Sengupta et al., 1993), Shetland Island, UK (Kingston et al., 1995), Straits of Johor (Abdullah et al.,1996), Arabian Gulf reports (Al-Lihaibi and Ghazi 1997), UAE coast research (Shriadah 1998), Bassein-Mumbai coast, India (Chouksey et al., 2004), Jiaozhou Bay, China (Wang et al., 2006), Gulf of Fos, France (Mille et al., 2007) Abu Dhabi, UAE (Abdet al., 2008) and Tamil Nadu coast, India (Veerasingam et al., 2010), Bufalo estuary, South Africa (Adeniji et al., 2017), Delaware River Estuary and Delmarva Peninsula, USA (Kim et al., 2018). The values observed Bouloubassi et al., (2001) at Changjiang estuary, China and Yunker and Macdonald (2003) at Fraser River Basin, Canada were most similar to the values of the present observation made at creek and coastal regions of Indian waters (Table 5).
Table 5
The petroleum hydrocarbon data were reported from selected coastal areas.
Location
|
PHC (Concentrations)
|
Reference
|
Arabian Sea along the Indian coast
|
0.6–5.8 ppm
|
Sengupta et al., 1993
|
Shetland Island, UK
|
7–8816 ppm
|
Kingston et al., 1995
|
Straits of Johor, Malaysia
|
0.7–36.7 ppm
|
Abdullah et al., 1996
|
Arabian Gulf
|
5.4–92.0 ppm
|
Al-Lihaibi & Ghazi, 1997
|
UAE coast
|
51,000 ppm
|
Shriadah, 1998
|
Changjiang estuary, China
|
2.2–11.82 ppm
|
Bouloubassi et al., 2001
|
Fraser River Basin, Canada
|
1.6–20.6 ppm
|
Yunker and Macdonald, 2003
|
Bassein-Mumbai coast, india
|
7.0–38.2 ppm
|
Chouksey et al., 2004
|
Jiaozhou Bay, China
|
0.54–8.12 ppm
|
Wang et al., 2006
|
Gulf of Fos, France
|
7.8–180 ppm
|
Miller et al., 2007
|
Abu Dhabi, UAE
|
6.14–62.7 ppm
|
Abd EL Gawad et al., 2008
|
Tamilnadu coast, India
|
1.48–4.23 ppm
|
Veerasingam et al., 2010
|
Bufalo estuary, eastern Cape Province, South Africa
|
12.59–1,100 µg g-1
|
Adeniji et al., 2017
|
Delaware River Estuary, USA
|
34–159 mg/kg
|
Kim et al., 2018
|
Delmarva Peninsula, Virginia USA
|
38–616 mg/kg
|
Kim et al., 2018
|
Saw Mill Creek, Staten Island, NewYork, USA
|
6524 to9586 mg/kg
|
Vane et al., 2020
|
Tamilnadu coast, India
|
2.05–17.47 µg g-1
|
Present study
|
The following order of contamination pattern of TPH was found for each location: Ennore creek > Ennore coastal > Tuticorin channel mouth > Tuticorin coastal.
The PCA was employed to concise the data analysis without changing the significance of data. From the analysis, it is evident that TPH, TOC and clay have significant positive loading at Station ENN-I and ENN-II (Fig. 3). The PCA further indicates that Ennore creek was highly contaminated with TPH as compared to other stations. In Tuticorin, the TPH, TOC, silt and clay were found to have positive loading in the stations TUT-I and TUT-II (Fig. 4). The results of the present study show close similarity with the reports made by Lyla et al., (2012).