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Variability of nature and composition of organic matter in the surficial sediments of mangrove and estuarine systems of Cochin were investigated. Assessment of biochemical composition and elements such as carbon, nitrogen and sulphur were employed for this. Irrespective of the higher content of total organic matter, the labile organic matter was very low in both mangrove and estuarine sediments. Concentrations of biochemical compounds were comparatively higher in mangrove sediments. Total lipids were the dominant class among labile organic compounds in both mangrove and estuarine sediments contributing 51.4% and 45.3%, respectively. Protein to carbohydrate ratio was higher in estuarine sediments when compared to mangroves, indicating low dead organic matter accumulation, probably due to the strong hydrodynamic conditions in estuaries. Correlation analysis showed that sediment texture had no significant correlation with any of the sedimentary parameters in mangroves, whereas in estuaries, it showed significant correlations with most of the sedimentary parameters. Principal component analysis indicated three different dominant processes in mangroves namely mangrove litter addition, diagenesis and other geochemical process like siltation and sorption/desorption, while in estuaries the dominant process seems to be diagenesis.

Phosphorus fractionation was employed to find the bioavailability of phosphorus and its seasonal variations in the Panangad region of Cochin estuary, the largest estuarine system in the southwest coast of India. Sequential extraction of the surficial sediments using chelating agents was taken as a tool for this. Phosphate in the water column showed seasonal variations, with high values during the monsoon months, suggesting external runoff. Sediment texture was found to be the main factor influencing the spatial distribution of the geochemical parameters in the study region. Similarly, total phosphorus also showed granulometric dependence and it ranged between 319.54 and 2,938.83 μg/g. Calcium-bound fraction was the main phosphorus pool in the estuary. Significant spatial variations were observed for all bioavailable fractions; iron-bound inorganic phosphorus (5.04-474.24 μg/g), calcium-bound inorganic phosphorus (11.16-826.09 μg/g), and acidsoluble organic phosphorus (22.22-365.86 μg/g). Among the non-bioavailable phosphorus, alkalisoluble organic fraction was the major one (51.92-1,002.45 μg/g). Residual organic phosphorus was K. R. Renjith (B) · N. Chandramohanakumar · M. M. Joseph Department of Chemical Oceanography, School of Marine Sciences, Cochin University of Science and Technology, Kochi 682016, Kerala, India e-mail: renjithaqua@gmail.com comparatively smaller fraction (3.25-14.64% of total). The sandy and muddy stations showed distinct fractional composition and the speciation study could endorse the overall geochemical character. There could be buffering of phosphorus, suggested by the increase in the percentage of bioavailable fractions during the lean premonsoon period, counteracting the decreases in the external loads. Principal component analysis was employed to find the possible processes influencing the speciation of phosphorus in the study region.

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The phosphorus fractions in three tropical mangrove systems of Cochin region were analysed by sequential extraction method. Iron-bound phosphorus was the major fraction in the first two stations, while station 3 was exclusively dominated by calcium-bound phosphorus. Compared to other stations, about tenfold increase in total phosphorus content was observed at station 3. This station is a congregation of communally breeding birds, and there is accumulation of bird guano. Mineralogical analysis showed the presence of monetite, a thermodynamically metastable calcium phosphate mineral, in this unique system. The excreta and carcass of the birds in this sanctuary seems to be the reason for the formation of monetite, which is favoured by periodic fluctuations in redox potential. The high mass percentages of calcium and phosphorus by XRF and SEM-EDS analysis confirm the existence of calcium phosphate mineral at station 3. First two stations did not show any noticeable difference in phosphorus fractions and inorganic fractions constituted to about 65% of total phosphorus. But at station 3, inorganic fractions were about 92%. Low C:P ratios and low organic phosphorus content indicated active mineralisation of phosphorus at station 3. Bioavailable fractions of phosphorus at stations 1 and 2 were about 75%, whereas 98% of the total phosphorus was bioavailable at station 3. Since the bulk of the total phosphorus is bioavailable, these mangrove sediments have the potential to act as source of phosphorus to the overlying waters.