M. Mohan et al/ Journal of Environment (2012), Vol. 01, Issue 01, pp.

1-6

ISSN 2049-8373

Research Paper

Sulphur Fractionation in the Sediments of Cochin Estuary

M.S. Shylesh Chandran 1, S. Sudheesh 1, E.V. Ramasamy 1 and Mahesh Mohan1*
1

School of Environmental Sciences, Mahatma Gandhi University, Kottayam, Kerala-686 560 *E-Mail: mahises@gmail.com

Abstract
Sulphur is an important redox element in the estuarine sediment and links with biogeochemical process of various elements. In the present study, anoxic sediment samples of Cochin estuary was undergone sequential chemical extraction in order to determine the contents of reduced sulphur species such as Elemental Sulphur (ES), Acid Volatile Sulphur (AVS), Cold Chromium Reducible Sulphur (CCRS), Hot Chromium Reducible Sulphur (HCRS). It was observed that Acid volatile Sulphides (AVS) are the second dominant fraction at the highly polluted region of the estuary. Sediments of other regions are dominated by CRS fractions (CCRS and HCRS). Temperature found to be significantly correlated with AVS, CCRS and HCRS. The results showed that the sediments of Cochin estuary have the potential for the production of both AVS and pyrites. It can be concluded that the transformation and mobility of toxic metals in the Cochin estuarine sediments may be affected by the sulphur chemistry. Keywords: Sulphur, Fractionation, Sediment, Cochin Estuary, AVS

1. Introduction
Sediments are ecologically important part of the aquatic habitat and also reservoir of contaminants, which play a significant role in maintaining the tropical status of any water body. The role of sediment in metal pollution is tied to factors like particle size, organic carbon, redox potential and elements. Lake bottom sediments comprise diverse sulphur forms. These compounds have substantial influence on the aquatic environment. Sulphur enters into numerous biogeochemical reactions in the aquatic environment. Among many sediment components, sulphur is the primary controller for trace metals in anoxic sediments. Many sediment bound metals are affected especially by the redox cycling of sulphur during early diagenesis (Howarth & Jorrgensen, 1984). Sulphur sequestration within sedimentary pyrite act as major sink for global biogeochemical cycle of sulphur and has subsequent impact on the carbon and oxygen cycles. Anaerobic sediment metabolism represents a significant pathway for carbon cycling in estuarine sediment. Sulphate reduction has been shown to be particularly important in the sulphur and carbon chemistry of highly productive shallow-water sub-tidal and salt marsh environments. Sulphur (S) is an abundant, multivalent non-metal and can found in various forms such as the pure element, sulphide and sulphate minerals. It is an essential element for life and is found in two amino acids: cysteine and methionine. The major sources of sulphur are: Soil, water and rocks contain sulphates, sulphides and organic sulphur and also the body of living organisms. The nature of the specific sulphur compound varies but it may be found as pyrites, acid volatile sulphur (AVS), elemental sulphur (ES), sulphates and organic sulphur. In sediments, iron sulphides are typically divided in to the following two groups: acid volatile sulphides (AVS), which are evolved via acid distillation and generally include amorphous forms [e.g., mackinawite (FeS), greigite (Fe3S4) and pyrrhotite (FeS)] and pyrite (FeS2) (Morse & Cornwell, 1987; Bates et al, 1993; Caron &

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M. Mohan et al/ Journal of Environment (2012), Vol. 01, Issue 01, pp. 1-6

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Kramer, 1994; Tack et al, 1997 and Billion et al, 2001). Chromium-reducible sulphur represents all inorganic reduced and intermediary oxidised sulphur i.e, iron monosulphides, pyrite (FeS2) and elemental sulphur (Tack et al, 1997). The difference between Cr2+-reducible S and AVS was therefore listed as intermediary oxidised Sulphur. Sulphur exists as variety of species in sediments and is involved to various degrees in the biogeochemistry of toxic metals. Sulphides are considered to be a key-binding phase involved in the biogeochemical cycling of heavy metals in anoxic sediments. In the present study, anoxic sediment samples of Cochin estuary were subjected to sequential chemical extraction in order to determine the contents of reduced S species such as elemental sulphur (ES), acid volatile sulphur (AVS), cold chromium reducible sulphur (CCRS) and hot chromium reducible sulphur (HCRS).

collected samples were immediately treated in situ by adding zinc acetate to fix easily oxidizable sulphides. All samples were tightly sealed in self-sealed plastic bags and kept in ice box at a temperature of 4 oC. One portion of the sediment sample was dried at 45 oC, finely grounded and sieved using 100 ASTM mesh and kept for geochemical analysis. Wet sediment samples were taken for sequential extraction of sulphur. 2.2. Sample Extraction and Analysis Samples for AVS analysis was analysed without drying due to their highly reactive nature and are handled under nitrogen in the laboratory to minimise oxidation of the samples. CRS analysis is best conducted on a dried and pulverised sample. The digestion procedures for the two methods differ slightly-AVS uses cold hydrochloric acid only as a reducing agent while CRS uses a much stronger reducing agent, chromous chloride, in addition to hot hydrochloric acid to reduce pyrite and elemental Sulphur (Canfield, 1986; 1998 and Tack et al, 1997). 2.3. Experimental Set Up The distillation apparatus used for extraction of the sulphur species consist of a digestion flask of

2. Materials and Methods

In the present study, the Cochin estuary and lower reaches of Periyar River that lies between latitude of 9 58-10 04 N and longitude 76 16-76 18 E were taken as study area (Figure 1).

Figure 1. Study Area Showing Sampling Locations

2.1. Sample Collection and Preservation Sediment samples were collected from eight sites of Cochin estuary by using Grab sampler. The

500 ml (Three necked round bottom flask). Top of the flask consists of three glass fittings for attachment of a condenser, a 50 ml syringe and a nitrogen bubbling tube. The top portion of the flask consists of ground glass

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M. Mohan et al/ Journal of Environment (2012), Vol. 01, Issue 01, pp. 1-6

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fittings. A section of glass tube connects from top of condenser to the sulphate trap. 2.3.1. Extractable Sulphate Extractable sulphate was determined by extracting 1 g of wet sediment with 50 ml of carbonate/ bicarbonate buffer in a polyethylene centrifuge tube. The solution was flushed with N2 gas and suspension was mechanically shaken for 1 hour. The supernatant liquid was analyzed for sulphate using spectrophotometer at 420 nm. 2.3.2. Acid Volatile Sulphur (AVS) 1 g of the sample taken into a reaction flask and the system was purged with N2 gas at a bubbling rate in the Zn-acetate traps of 1-2 bubbles per second for 10 minutes before the introduction of reagents. Then 10 ml of 12N HCl was added to the reaction flask. After 5-10 minuets, the system was brought to boil for 1 hour. Then zinc acetate trapping solution was removed and titrated. 2.3.3. Chromium Reducible Sulphur (CRS) CRS was determined by modified method of Canfield et al, 1986 and 1998. Two fractions of CRS were estimated Cold Chromium Reducible Sulphur (CCRS) (less mature pyrites) and Hot Chromium Reducible Sulphur (HCRS) (mature pyrites). The sediment after the extraction of AVS is used for analysis of CRS (Burton et al, 2008). 2.3.4. Cold Chromium Reducible Sulphur (CCRS) After the removal of AVS, 10 ml of ethanol and 40 ml of CrCl2 (prepared according to Kolthoff & Sandell,1963) was added to the reaction flask and the system was flushed with N2 gas, after 10-15 minutes the trap was removed and determined by iodometric titration . 2.3.5. Hot Chromium Reducible Sulphur (HCRS) After the removal of CCRS, the system was brought to boil for 1 hour. After boiling the trap was removed and titrated by iodometric method. 2.3.6. Total Sulphur Total sulphur was determined with nitric acid digestion in microwave digester and detection with Inductively Coupled Plasma Atomic Emitting Spectrometer (ICPAES).

sediment samples. The concentration of ES ranged from 1055 ppm to 610 ppm. The maximum value recorded from the site-8 which is downstream of in the industrial area. The mean concentration obtained was 854.13 ppm. AVS has showed high variability and the values ranged from 96 to 3336 ppm, and the maximum value was noticed at the S8. The mean value of AVS was 1207. The CCRS ranged between 632 ppm and 5592 ppm. The mean value was 3055 ppm. The HCRS concentration in the estuarine sediments varied from 896 ppm to 3336 ppm with a mean value of 1926 ppm. The analytical results of geochemical parameters like pH, organic carbon, iron, temperature and moisture content of the sediment were given in Table 2 pH varied from 4.48 (S -8) to 6.87 (S-6) with an average value of 6.20. Sediments were slightly acidic at the region of industrial outlets. The high organic carbon content was found at S-7 (6%) where as low concentration has noticed at S-4 (2.4%) (Table 2) and the mean OC were 4.7%. High temperature was observed for the upstream sediments (34.6-36.3 oC), which are very near to the industrial outlets compared with the downstream region. The maximum and minimum temperature observed was 36.3 oC and 29.8 oC respectively. Moisture content varied between sites. The mean moisture content of sediment was 61.80%.

4. Discussion
The various sulphur fractions observed at different sites are in the order (Figure 2). S1: S2: S3: S4: S5: S6: S7: S8: CCRS > HCRS > ES > AVS HCRS > CCRS > ES > AVS CCRS > HCRS > ES > AVS CCRS > HCRS > ES > AVS CCRS > HCRS > ES > AVS CCRS > HCRS > AVS > ES CCRS > AVS > HCRS > ES CCRS > AVS > HCRS > ES

High percentage was observed for CCRS in all the samples except S2, where HCRS fraction showed high concentration. Major part of the sulphur concentration was shared between CCRS and HCRS in the downstream samples (S 1 S 6). But for the upstream samples (S 7-S 8) instead of HCRS, AVS hold the major position after CCRS. AVS showed low concentration for all the samples collected from the down stream region of the study area (S1- S5). The high HCRS fraction at S2 might be due to the high rate of pyritization than the other regions. Availability of reactive iron, low AVS and less concentration of sulphurscavenging metals may be attributed to the transformation

3. Results
The results are presented in wet weight basis (Table 1). Total Sulphur content (TS) was analyzed in sediments. Presence of Elemental Sulphur was observed in all the

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M. Mohan et al/ Journal of Environment (2012), Vol. 01, Issue 01, pp. 1-6

ISSN 2049-8373

of CCRS to HCRS. The high concentration of HCRS and CCRS at station 1-6 confirmed that the process of pyritization was maximum at lower region of the study area i.e, near to the barmouth region. It may be dominated by FeS2 formed during oxidation of sediment.
Table 1. Shows Fractionations of Sulphur in Sediment (ppm wet wt.)

Pyrite provides an important sink for sulphur and trace metals in salt marsh sediments and in estuarine/marine sediments in general (Lord III, 1982). But in the upstream sediments the influence of AVS was maximum on the sulphur chemistry and thus the rate of formation of mature

Samples S1 S2 S3 S4 S5 S6 S7 S8 Mean

ES 846 612 991 833 916 970 610 1055 854.13

AVS 96 336 430 97 376 1696 3296 3336 1207.88

CCRS 3376 632 3056 5592 1376 3256 3656 3496 3055

HCRS 1456 896 1659 3336 1056 2096 1736 3176 1926.38

Sum of Sulphur Fractions 5774 2476 6136 9858 3724 8018 9298 11063 7043.38

Total Sulphur 6645 3841 6257 8002 6857 9204 5184 8167 6769.63

Table 2. Geo-Chemical Parameters of Sediment Samples

Samples S1 S2 S3 S4 S5 S6 S7 S8 Mean
100% 90% 80% 70% 60% % 50% 40% 30% 20% 10% 0% S 1

pH 6.65 6.20 6.85 6.60 5.97 6.87 5.99 4.48 6.20

Organic Carbon (%) 3.68 4.77 5.7 2.4 5.3 3.27 6 3 4.27

Moisture (%) 60.48 67.10 63.15 46.78 60.49 50.81 71 74.6 6.18

Temperature (oC ) 29.8 29.9 29.9 34.3 29.8 34.6 36.3 35.3 32.48

Iron (%) 3.41 3.15 3 4.05 2.85 3.36 3.63 3.44 3.36

HCRS

CCRS

AVS

ES
S 2 S 3 S 4 S 5 S 6 S 7 S 8

Sample No.

Figure 2. Percentage of Sulphur Fractions in the Sediments

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M. Mohan et al/ Journal of Environment (2012), Vol. 01, Issue 01, pp. 1-6

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pyrite is less. This might be due to various factors such as anoxic conditions, high concentration of S compounds, reactive iron etc. The low concentration of AVS in the lower region can be owed to the increased pyritization process. High anoxic condition at the sedimentary environment may be the reason for the formation of CCRS from the AVS. The sediment sample of upper reaches of the study area showed slightly acidic character. High organic carbon percentage was also observed for the sediments during the study.

can thrive and make use of sulphate instead of oxygen for organic matter mineralisation which will enhance the production of sulphide. CRS fractions also showed positive correlation with iron. Among the various fractions AVS is the most significant one. AVS can affect the biogeochemical cycle of various trace elements. The formation and accumulation of inorganic sulphur and other sulphur fractions are typical for polluted sediment and can be related to a large influx of

Table 3. Correlation Matrix for Sulphur Fractions and Geochemical Parameters

Parameters pH Temperature OC Fe ES AVS CCRS HCRS

pH 1 -.366 .112 -.004 -.168 -.657 .097 -.326

Temperature 1 -.317 .677 -.009 .798(*) .610 .695

OC

Fe

ES

AVS

CCRS

HCRS

1 -.481 -.386 .057 -.533 -.729(*)

1 .220 .299 .956(**) .769(*)

1 .037 .223 .426

1 .179 .354

1 .825(*)

* Correlation is significant at the 0.05 level (2-tailed) ** Correlation is significant at the 0.01 level (2-tailed)

Pearsons correlation between sulphur fractions and some physiochemical parameter of sediments were calculated (Table 3). Temperature found to be significantly correlated with AVS, CCRS and HCRS i.e., the sulphate reducing activity increases with increase in temperature as observed. CRS (CCRS & HCRS), the most predominant reduced inorganic sulphur pool in sediments showed inverse correlation with organic carbon. But a positive correlation was observed between AVS and OC. The increase in organic carbon or matter can enhance the production of AVS, if other factors like oxic/anoxic conditions favours. AVS is the most biogeochemically active part which is having an eco-toxicological significance because of its affinity with divalent heavy metals. The high AVS concentrations in the upper stations indicated the existence of moderate sulphur reducing condition. The high AVS content could reduce the mobility of metals in that area, though the area is well known for heavy metal contamination (Holmer & Bondgaar, 2011). AVS showed a significant positive correlation with temperature and negatively correlated with pH. The low concentration of AVS may reduce the scavenging effect on the metal species in the lower reaches of the study area. CCRS and HCRS showed inverse correlation with organic carbon. At high organic carbon condition anoxic microbes like sulphur reducing bacteria, Fe reducing bacteria etc.

heavy metals.

5. Conclusion
The studies on sulphur chemistry are highly significant as it is mainly linked with the transformation and mobility of various toxic pollutants. In the present study Acid volatile Sulphides (AVS) was the second dominant fraction at the highly polluted region. Sediments of other regions are dominated by CRS fractions (CCRS and HCRS). The results showed that the sediments of Cochin estuary have the potential for the production of both AVS and pyrites. It can be concluded that the transformation and mobility of toxic metals in the Cochin estuarine sediments may be influenced by the sulphur chemistry. More studies are needed to understand the relation between sulphur fraction and the toxic metal geochemistry in the Cochin estuary.

Acknowledgement
The financial support from Ministry of Earth Sciences (MoES), GOI through their project (No.MoES/8/PC/2(3)/ 2007-PC-IV) is gratefully acknowledged.

References
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