Polychlorinated biphenyls in the surface and deep waters of the Southern Indian Ocean and Coastal Antarctica.

Polychlorinated biphenyl compounds (PCBs) are industrial chemicals whose production was discontinued in the early nineties in most countries. Sill, PCBs are detectable in pristine and remote locations. Occurrence in regions such as Southern Oceans and Antarctica are influenced by the global, and regional, cycling. Here, we studied the surface and deep ocean distribution of indicator- and dioxin-like PCB congeners in the Southern Indian Ocean (SIO), and the coast of Antarctica (COA) during the tenth Indian Southern Ocean Expedition (SOE-10), December 2017-February 2018. ∑21PCBs in SIO surface waters ranged from 3.8 to 167.1 pg L-1 (average ± standard deviation: 35.7 ± 48.4 pg L-1), and in COA from 1.0 to 41.8 pg L-1 (13.8 ± 12.7 pg L-1), respectively. A noticeable gradient was observed, with higher PCBs levels in northern latitudes than southern latitudes in the SIO, and higher levels in the eastern longitudes compared to western longitudes in the COA. Results suggest the influence of secondary sources, or re-emission, of PCBs in the Southern Oceans and Antarctica. Both regions showed notable PCB levels in surface and deep waters (up to 1000 m) due to ongoing surface sources and remineralization processes in deeper waters. Multimedia modeling with the global model (BETR-Global) suggests the SIO act as a net sink for PCBs in the ocean.

Distribution of organochlorine pesticides in surface and deep waters of the Southern Indian Ocean and coastal Antarctic waters.

Antarctica is a remote and pristine region. Yet it plays a vital role in biogeochemical cycles of global anthropogenic contaminants, such as persistent organic pollution (POPs). This work reports the distribution of legacy and new POPs in surface and depth profiles/deeper water of the Southern Indian Ocean (SIO) and the coast of Antarctica (COA). Samples were collected during the 10th Indian Southern Ocean expedition (SOE-10) in the year 2017. Concentrations of ∑HCH (hexachlorocyclohexane), ∑DDT (dichlorodiphenyltrichloroethane), and ∑ENDO (endosulfan) in surface seawater from the SIO region ranged between not detected (ND) to 1.21 pg/Liter (pg L-1) (average. ± s.d.: 0.35 ± 0.42 pg L-1), ND to 1.83 pg L-1 (0.69 ± 84 pg L-1), and ND - to 2.06 pg L-1 (0.56 ± 0., 88 pg L-1), respectively. The concentrations of ∑HCH, ∑DDT, and ∑ENDO in COA ranged from ND to 0.98 pg L-1 (0.25 ± 0.27 pg L-1), ND to 3.61 pg L-1(0.50 ± 1.08 pg L-1), and ND to 2.09 pg L-1 (0.45 ± 0.84 pg L-1), respectively. Concentrations of isomers of endosulfan, and largely of HCHs, suggested an aged source. Some concentration ratios of α-to γ-HCH were close to 1, indicating a contribution from ongoing sources. Results indicate the important role of ocean currents in mediating the transport and detection of OCPs. As such, OCPs dynamics in deeper oceans may play an important role in OCPs cycling in the marine environment.

An insight into mercury reduction process by humic substances in aqueous medium under dark condition.

Mercury (Hg) reduction by humic substances (HS) in the aquatic medium under the dark condition is a poorly understood but important process in Hg biogeochemical cycling. In this study, an effort was made to provide a better understanding of Hg(II) reduction by well-characterized humic substances under dark condition. Reduction of Hg(II) by dissolved HS in aquatic systems increases with increasing Hg loading. However, Hg(II) reduction gradually decreases with the increasing total S content and oxygen containing functional groups in the dissolved HS under dark condition. Increasing major cation concentration decreases the rate of Hg(II) reduction in aquatic systems. High concentration of Ca2+ ion slows down the intermolecular electron transfer from HS to Hg(II) and inhibits the formation of Hg0 in absence of light. This study indicates that complexation of Hg(II) and HS is essential for Hg reduction under dark condition.

Mercury profiles in sediment from the marginal high of Arabian Sea: an indicator of increasing anthropogenic Hg input.

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.

Partitioning of metals in different binding phases of tropical estuarine sediments: importance of metal chemistry.

Distribution of metals in different binding phases of estuarine sediments provides chemically significant description of metal-sediment interactions. This study describes the influences of ligand field stabilization energy (LFSE), Jahn-Teller effect, and water exchange rate (k-w) on metal distribution in different binding phases of estuarine sediments. It was found that Cu had highest affinity for organic binding phases in the studied sediments followed by Ni and Pb. However, Pb showed strong association with Fe/Mn oxide phases followed by Ni and Cu. Faster k-w of Cu (II) (1 × 10(9) s(-1)) increased the rate of complex formation of Cu(2+) ion with ligand in the organic phases. The Cu-ligand (from organic phase) complexes gained extra stability by the Jahn-Teller effect. The combined effects of these two phenomena and high ionic potential increased the association of Cu with the organic phases of the sediments than Ni and Pb. The smaller ionic radii of Ni(2+) (0.72 Å) than Pb(2+) (1.20 Å) increase the stability of Ni-ligand complexes in the organic phase of the sediments. High LFSE of Ni(II) (compared with Pb(2+) ions) also make Ni-organic complexes increasingly stable than Pb. High k-w (7 × 10(9) s(-1)) of Pb did not help it to associate with organic phases in the sediments. The high concentration of Pb in the Fe/Mn oxyhydroxide binding phase was probably due to co-precipitation of Pb(2+) and Fe(3+). High surface area or site availability for Pb(2+) ion on Fe oxyhydroxide phase was probably responsible for the high concentration of Pb in Fe/Mn oxyhydroxide phase. Increasing concentrations of Cu in organic phases with the increasing Cu loading suggest that enough binding sites were available for Cu in the organic binding phases of the sediments. This study also describes the influence of nature of sedimentary organic carbon (terrestrial and marine derived OC) in controlling these metal distribution and speciation in marine sediment.

Reduction of mercury (II) by humic substances--influence of pH, salinity of aquatic system.

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.

Fate of copper complexes in hydrothermally altered deep-sea sediments from the Central Indian Ocean Basin.

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.

Mercury speciation in coastal sediments from the central east coast of India by modified BCR method.

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.