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Sedimentary organic matter (SOM) plays an important role in hosting and reducing HgII in marine/estuarine sediment. This study provides a better understanding on the influence of nature of SOM, in regulating sedimentary mercury (Hg) and elemental mercury (Hg0) distribution, and speciation in the Zuari and Mandovi Estuaries that are representative of monsoon fed tropical estuaries, located in the central west coast of India. Salinity of the overlying water column controlled the physical and chemical characteristics of SOM in the estuarine systems. The high molecular weight (MW) SOM dominated at the mid and upstream (low salinity region) of the estuaries, whereas, the low MW SOM prevailed at the downstream (high salinity region). Sediment Hg showed more affinity towards the SOM of high MW. Increasing MW of SOM increased total sedimentary HgT in both the estuaries. SOM with low MW in the estuarine sediment displayed a negative relationship with the sediment Hg concentration. Distribution of Hg0 concentration in the estuarine sediment suggests that reduction of HgII in presence low MW SOM was a dominant process. It was also found that distribution and speciation of Hg0 in the estuarine sediment depends on the quantity, quality of the SOM, and the total sediment Hg loading. This study demonstrated that the competition between Hg-SOM complexation and HgII reduction by SOM controls HgII/Hg0 distribution in tropical estuarine sediment systems.

There is limited knowledge regarding seawater intrusion on Hg distribution in monsoon fed tropical estuarine systems during dry season (February to May). This study examined the influence of resuspension of estuarine sediment and intrusion of Hg bound SPM (HgSPM) (by the tide) from the outside of an estuary in controlling distribution, mobility, and bioavailability of Hg within the estuarine systems during the dry season. This investigation was carried out in the Mandovi estuary, a monsoon fed tropical estuary from the central west coast of India. Total Hg concentrations in the water column showed an increasing trend from upstream to downstream of the estuary. The concentration of Hg in the water column of the estuary was much below the concentration recommended by the EPA for aquatic life ambient water quality. Dissolved Hg (HgDissolved) was found to associate mainly with the higher molecular weight fraction of dissolved organic matter (DOM). A significant portion of the total Hg in the water column was present as HgSPM. The average bio-accumulated Hg concentration in edible oyster was high (collected from the estuary) during the dry season compared to the wet season (June to September). This study reveals that resuspension of Hg associated finer sediment particles and intrusion of HgSPM from the outside of the estuary may increase bioavailability of Hg in the Mandovi estuarine systems during the dry season. It is suggested that Hg bioaccumulation in commercially important biological species from different tropical estuarine system may increase during the dry season. The outcome of this research can be useful for policy making and to take proper decision to reduce and control Hg/toxic metals pollution (if any) in tropical estuarine system.

Geochemical fractionation study of cadmium (Cd) in combination with equilibrium based chemical speciation modelling (visual MINTEQ) in finer sediment samples (silt and clay portion), provided a better description of Cd bioavailability for sessile organisms (like oysters) in the Zuari estuary, west coast of India. A substantial fraction of total Cd in the finer sediment samples was present as water soluble, exchangeable and carbonate/bicarbonate forms and showed a strong positive relationship with Cd-bioaccumulation in oysters (Magallana sp.) from the study area. Cadmium bioaccumulation (ranged from 2.4–7.9 mg·kg−1) in soft tissues of the edible oyster was high (higher than the maximum permissible limit for human consumption) throughout the study period of one year. Equilibrium based speciation modelling suggest that sedimentary CdCl2, CdCl+ and Cd2+ were responsible for Cd bioaccumulation in the oysters. This study describes that combination of geochemical fractionation study of metals in finer sediments and equilibrium based speciation modelling can be very useful in comprehending link between sedimentary metal speciation and its bioaccumulation in sessile organisms.

Sedimentary organic matter (SOM) plays an important role in hosting and reducing Hg

A linkage between Cd speciation in sediments and its bioaccumulation in edible oyster (Crassostrea sp.) from a tropical estuarine system was established. Bioaccumulation of Cd in edible oyster increased with the increasing lability and dissociation rate constants of Cd-sediment complexes in the bottom sediments. Total Cd concentration in sediment was not a good indicator of Cd-bioavailability. Increasing trace metal competition in sediments increased lability and bioavailability of Cd in the tropical estuarine sediment. Low thermodynamic stability and high bioavailability of Cd in the estuarine sediment were responsible for high bioaccumulation of Cd in edible oysters (3.2-12.2mgkg(-1)) even though the total concentration of Cd in the bottom sediment was low (0.17-0.49mgkg(-1)).

Impact of pH variation of overlying water column on transport and transformation of Cu-sediment complexes in the bottom mangrove sediments was investigated by using different metal extraction studies. The total Cu concentration in the studied sediments varied from ~64 ± 1 to 78 ± 2 mg·kg−1. The sequential extraction study showed that a major part of the sedimentary Cu (85–90% of the total sedimentary Cu) was present within the structure of the sediments with minimum mobility and bioavailability. The redistribution of non-residual Cu among the different binding phases of the sediments was observed at different pH. It was found that Cu shifted from the different non-residual binding phases to the organic binding phase of the sediments at higher pH. Partial leaching of sedimentary Cu-SOM complexes (with increasing stability as determined by kinetic extraction study) was observed at higher pH. This study infers that increase in pH of overlying water column may release Cu-SOM complexes and increase the mobility of Cu-complexes in mangrove systems.

This study investigated the linkage between mercury (Hg) speciation in the surficial sediments from a mangrove ecosystem of the Zuari Estuary, west coast of India, with Hg bioaccumulation in gastropods collected from the same area. Multiple operationally defined protocols and methods were used for determination of Hg speciation study in the mangrove sediments. Moderately low concentrations of Hg were observed in the sediments, ranging from 37.3 ± 1.9 to 79.6 ± 4.0 µg/kg. Geochemical fractionation showed that a significant part of sedimentary Hg was present within the structure of the sediment (residual fraction) and not bioavailable. Non-residual Hg was primarily associated with oxidizable (sedimentary organic matter (SOM) or sulfide) binding phase of the sediments, and ranged from 9.2 ± 0.3 to 78.5 ± 3.9 µg/kg. Concentration of methylmercury (MeHg) (a neurotoxin) in the sediments varied from 1.7 ± 0.1 to 4.4 ± 0.1 µg/kg. l-Cysteine, a suitable complexing ligand, extractable Hg concentration in the sediments ranged from 4.3 ± 0.1 to 15.9 ± 0.3 µg/kg. Statistical analysis suggested that MeHg was adsorbed on Fe/Mn oxyhydroxide phases in the sediments. l-Cysteine was found to extract sedimentary MeHg and thermodynamically less stable Hg-SOM complexes from the sediments. Concentrations of bioaccumulated Hg in soft tissues of the gastropod, Pirenella cingulata, ranged from 57.6 ± 4.4 to 224.4 ± 7.2 µg/kg. Positive correlations existed between the concentration of bioaccumulated Hg in the gastropods and the concentrations of Hg associated with the oxidizable phase, sedimentary MeHg and l-Cysteine extracted Hg in the sediments. This study indicated that operationally defined Hg species can be useful in estimating bioavailable Hg to obligatory deposit feeder in tropical mangrove systems.

This is the first study to describe distribution and speciation of Hg in coastal sediments from the central east coast of India. The concentrations of Hg in the studied sediments were found to be much lower than the Hg concentration recommended in coastal sediments by the United State Environmental Protection Agency and the Canadian Council of Ministers of the Environment for the protection of aquatic life. This study suggests that the interactions between Hg and coastal sediments are influenced by particle size (sand, silt and clay) of the sediments and the total organic carbon (TOC) content in the sediments. It was found that the coastal sediments from the central east coast of India could act as a sink for Hg. The availability of strong uncomplexed-Hg binding sites in the coastal sediments was observed.

Interactions of mercury (Hg) with different molecular weight fractions of humic substances (HS) play an important role in controlling distribution, diffusion, speciation, and bioavailability of Hg in natural systems. This study suggests that Hg prefers to associate with higher molecular weight fractions of HS and this association particularly predominates at low pH and high ionic strengths of the medium. The concentrations of aggregated HS (with higher molecular weight) become high at lower pH (acidic condition) and high ionic strength. Molecular weight of HS gradually decreases with the increasing pH (basic condition) and low ionic strength of the medium. The disaggregation property of HS which involves the release of monomers from the surface of the aggregates produces HSs of different intermediate molecular weight with different Hg complexing capacity. Distribution of Hg in different molecular weight fractions of HS is dependent on aggregational and disaggregational properties of HS in aquatic medium. Association of Hg with high molecular weight fraction of HS may alter distribution and bioavailability of Hg in a system as the bioreactivity of organic matter decrease along a continuum of size in aquatic medium.

Total Hg distributions and its speciation were determined in two sediment cores collected from the western continental marginal high of India. Total Hg content in the sediment was found to gradually increase (by approximately two times) towards the surface in both the cores. It was found that Hg was preferentially bound to sulfide under anoxic condition. However, redox-mediated reactions in the upper part of the core influenced the total Hg content in the sediment cores. This study suggests that probable increase in authigenic and allogenic Hg deposition attributed to the increasing Hg concentration in the surface sediment in the study area.

This study demonstrates that under abiotic dark conditions in aquatic system, humic substances are not only capable of converting Hg(II) to Hg(0) but also able to bind Hg(II) ion. The degree of Hg(II) reduction is significantly influenced by the ratio of -COOH/-OH groups and the sulfur content in the HS, revealing a strong competition between complexation and reduction of Hg(II). This study suggests that abiotic and dark Hg(II) reduction depends on the pH and salinity of aqueous medium. At lower pH (∼ 4.0) and lower salinity (≤ 5.0 PSU), the reduction of Hg(II) to elemental mercury (Hg(0)) was comparatively rapid. Higher -COOH/-OH ratios in HS, favors dark abiotic reduction of Hg(II) as did a lower sulfur (S) content of HS. This study provided a rigorously controlled experimental design that showed that dark abiotic Hg(II) reduction by HS can potentially be important in the aquatic environment and is independent of the photochemical reduction observed in both fresh water and sea water.

The current study aims to understand the speciation and fate of Cu complexes in hydrothermally altered sediments from the Central Indian Ocean Basin and assess the probable impacts of deep-sea mining on speciation of Cu complexes and assess the Cu flux from this sediment to the water column in this area. This study suggests that most of the Cu was strongly associated with different binding sites in Fe-oxide phases of the hydrothermally altered sediments with stabilities higher than that of Cu-EDTA complexes. The speciation of Cu indicates that hydrothermally influenced deep-sea sediments from Central Indian Ocean Basin may not significantly contribute to the global Cu flux. However, increasing lability of Cu-sediment complexes with increasing depth of sediment may increase bioavailability and Cu flux to the global ocean during deep-sea mining.