S in Marine Sediments

Horvat M, Mandic V, Liang L, Bloom NS, Padberg S, Lee Y.-H, Hintelmann H, and Benoit J (1994) Certification of methylmercury compounds concentration in marine sediment reference material, IAEA-356. Appl Organomet Chem 8 533-540. 

Pavlou, S.P (1987) The use of equilibrium partition approach in determining safe levels of contaminants in marine sediments, p. 388 -12. In Fate and Effects of Sediments-Bound Chemicals in Aquatic Systems. Dickson, K.L., Maki, A.W., Brungs, W.A., Editors. Proceedings of the Sixth Pellston Workshop, Florissant, Colorado, August 12-17,1984. SETAC Special Publ. Series, Ward, C.H., Walton, B.T., Eds., Pergamon Press, N.Y. 

Braddock, J.F. and Z. Richter. 1998. Microbial Degradation of Aromatic Hydrocarbons in Marine Sediments. U.S. Dept. Interior, OCS Study MMS 97-0041. 82 pp. 

Malins, D.C., M.M. Krahn, D.W. Brown, L.D. Rhodes, M.S. Myers, B.B. McCain, and S.L. Chan. 1985a. Toxic chemicals in marine sediment and biota from Mukilteo, Washington relationships with hepatic neoplasms and other hepatic lesions in English sole (Parophrys vetulus). Jour. Natl. Cancer Inst. 74 487-494. 

Keir, R.S., and R.L. Michel. 1993. Interface dissolution control of the C profile in marine sediment. Geochimica et Cosmochimica Acta 57 3563-3573. 

Hagiwara Y (2000) Selenium isotope ratios in marine sediments and algae. A reconnaissance study. M.S. 

In terms of organic carbon generation, the coccolithophorids are a minor player, representing only 6 to 8% of global marine primary production. But their detrital remains contribute disproportionately to the burial of carbon in marine sediments. This is due to near complete loss of POC via remineralization as the detrital hard and soft parts settle to the seafloor. As estimated from Broecker s Box model in Chapter 9, only about 1% of the POM that sinks out of the surfece water is buried in marine sediments. In comparison, about 20% of the biogenic PIC survives to become buried in the sediments. 

In the preceding sections, we have discussed the marine processes that control calcium carbonate s formation, dissolution, and delivery to the seafloor. Their combined effects determine the geographic distribution of calcium carbonate in marine sediments seen in Figure 15.5. As noted earlier, the global distribution of calcareous sediments does not seem to follow that of plankton production. This points to the overriding importance of the processes that control the dissolution and sedimentation of calcium carbonate. 

Figure 1. Data from the literature indicate that S concentrations in surface lake sediments are poorly correlated with A, lake-water sulfate concentrations (104 lakes) B, sediment carbon content (78 lakes) or C, sediment iron content (22 lakes). Sulfur concentrations in lake sediments typically are lower than concentrations in marine sediments of comparable carbon content (upper line in B). The lower line in B represents the average C S ratio (55) reported in seston (59, 72, 27, 56, 78). Most of the lake sediments reported in the literature have more iron than sulfur. (Data are from references 24-30, 34, 48—51, 55-57, 59-61, 71, 104, 112, 199, 205, 222, and 223.)...

Iron frequently has been postulated to be an important electron acceptor for oxidation of sulfide (58, 84,119, 142, 152). Experimental and theoretical studies have demonstrated that Fe(III) will oxidize pyrite (153-157). Reductive dissolution of iron oxides by sulfide also is well documented. Progressive depletion of iron oxides often is coincident with increases in iron sulfides in marine sediments (94, 158, 159). Low concentrations of sulfide even in zones of rapid sulfide formation were attributed to reactions with iron oxides (94). Pyzik and Sommer (160) and Rickard (161) studied the kinetics of goethite reduction by sulfide thiosulfate and elemental S were the oxidized S species identified. Recent investigations of reductive dissolution of hematite and lepidocrocite found polysulfides, thiosulfate, sulfite, and sulfate as end products (162, 163). 

Reineke N, Biselli S, Franke S, Franke W, Heinzel N, Hiihnerfuss H, Iznaguen H, Kammann U, Theobald N, Vobach M, Wosniok W (2006) Brominated Indoles and Phenols in Marine Sediments and Water Extracts from the North and Baltic Seas - Concentrations and Effects. Arch Environ Contam Toxicol 51 186... 

Much of what is currently known about the Earth s climate comes from the application of stable isotopes collected from ocean drill cores in marine sediments (e.g., Zachos et al. 2001). These isotopic data sets provide detailed records of how the Earth s oceans have responded to changing climate and are extremely valuable in assessing global climate histories down to millennial scales. Similar detailed isotopic records for terrestrial systems are, however, uncommon and frequently continuous terrestrial climate records that span millions to tens of millions of years are not preserved in the terrestrial geologic record. With the advent of paleoaltimetry studies targeted directly at the coupled isotopic effects of changes in climate... 

Fallon, R.D., Newell, S.Y. and Hopkinson, C.S., 1983. Bacterial production in marine sediments will cell-specific measures agree with whole-system metabolism. Mar. Ecol. Prog. Ser., 11 119-127. 

Koh, C.H., Khim, J.S., Kannan, K., Villeneuve, D.L., Giesy, J.P., 2006a. Characterization of trace organic contaminants in marine sediment from Yeongil Bay, Korea 1. Instrumental analyses. Environ. Pollut. 142, 39-47. 

PCBs, polybrominated diphenyl ethers (PBDEs) and OCPs were reported in Singapore s coastal marine sediments by Wurl and Obbard (2005b) and concentration levels are summarized in Table 15.5 (PCBs and PBDEs) and Table 15.6 (OCPs). Sample stations are indicated in Fig. 15.12.Total PCB concentrations ranged widely from 1.4 to 329.6 ngg-1. High concentrations were found in samples close to highly industrialized areas dominated by petrochemical plants. A notable decline in the concentration of EPCBs could be observed seawards from sample station SW3 over SW2 to SW1 (62.2-14.1 ng g-1) (Fig. 15.12) and... 

A comparison of the concentration of PCBs and OCPs in Singapore s coastal marine sediments with the sediment quality guideline specified by the USEPA (1997) and the Canadian Council of Ministers of the Environment (CCME, 2002) (Table 15.8), and comparison with levels of contaminants reported from other locations in Asia, Singapore s marine sediments can be classified as moderately contaminated with probable ecotoxicological impacts to marine organisms. 

Wurl, O., Obbard, J.P., 2005b. Organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in Singapore s coastal marine sediments. Chemosphere 58, 925-933. 

Burgess, R.M., Pelletier, M.C., Ho, K.T., Serbst, J.R., Ryba, S.A., Kuhn, A., Perron, M.M., Raczelowski, P. and Cantwell, M.G. (2003) Removal of ammonia toxicity in marine sediment TIEs a comparison of Ulva lactuca, zeolite and aeration methods, Marine Pollution Bulletin 46, 607-618. 

The Michael addition mechanism, whereby sulfur nucleophiles react with organic molecules containing activated unsaturated bonds, is probably a major pathway for organosulfur formation in marine sediments. In reducing sediments, where environmental factors can result in incomplete oxidation of sulfide (e.g. intertidal sediments), bisulfide (HS ) as well as polysulfide ions (S 2 ) are probably the major sulnir nucleophiles. Kinetic studies of reactions of these nucleophiles with simple molecules containing activated unsaturated bonds (acrylic acid, acrylonitrile) indicate that polysulfide ions are more reactive than bisulfide. These results are in agreement with some previous studies (30) as well as frontier molecular orbital considerations. Studies on pH variation indicate that the speciation of reactants influences reaction rates. In seawater medium, which resembles pore water constitution, acrylic acid reacts with HS at a lower rate relative to acrylonitrile because of the reduced electrophilicity of the acrylate ion at seawater pH. 

Ryba, S.A. and R.M. Burgess. 2002. Effects of sample preparation on the measurement of organic carbon, hydrogen, nitrogen, sulfur, and oxygen concentrations in marine sediments. Chemosphere 48 139-147. 

The other major reactant in Equation 1 is sulfate (SO42 ). Sulfate concentrations are highly variable in lake waters, from 3 x 10 5 mol/L in soft-water lakes in crystalline-rock drainage basins to 1.6 mol/L in hypersaline lakes (2.). In productive, freshwater lakes, sulfate reduction typically goes nearly to completion (5.). As sulfate concentrations increase, amounts of organic matter eventually become insufficient for complete sulfate reduction to occur. This is the case in "normal" marine sediment where a linear relation between total reduced sulfur and organic-carbon concentrations is observed. Sea-water sulfate concentration is 0.028 mol/L and the ratio of total reduced sulfur to organic-carbon concentrations (often referred to as S/C) in marine sediment is 0.33 ( ). ... 

Nipper, M., Qian, Y., Carr, R.S., Miller, K. (2004) Degradation of picric acid and 2,6-DNT in marine sediments and waters the role of microbial activity and ultra-violet exposure. Chemosphere 56, 519-530. 

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