Metals in suspended matter and bottom sediments from of North Dvina estuary

In 1995-1997 three oceanographic cruises to the White Sea were undertaken in the framework of the INTAS project 94-391, and a multi-disciplinary geochemical study of the major North Dvina estuary has been carried out. Distribution of temperature, salinity and concentration of suspended matter in water columm, as well as contents of Al, Fe, Mn, Co, Cu, Ni, Cr, Pb, Zn, and organic carbon contents in suspended matter and sediments of the North Dvina estuary were determined. Most of the metals and organic matter studied appear to be of terrestrial origin, since the main source of investigated elements in the estuary is river run-off. It was found that metals incorporated in minerals are absolutely prevailing forms in estuarine sediments, they comprise up to 60-99% of total metal contents. Two zones of metal accumulation in the sediments were found in the North Dvina estuary. These zones are considered as local geochemical barriers within a major river-sea barrier. Distribution of most elements studied in the sediments of the North Dvina estuary is controlled by grain size variability in the sediments. Analysis of data on heavy metal contents in the sediments and bivalves of the North Dvina estuary did not reveal any anthropogenic heavy metal pollution in the region.

Concentrations and accumulation rates of platinum-group elements and rhenium in Pacific and Atlantic sediments, DSDP and ODP data

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of ~1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by ~95% relative to chondritic Ir proportions. A similar depletion in Os (~90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The ~1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over ~65 Ma, the effective diffusivities are ~10**?13 cm**2/s, much smaller than that of soluble cations in pore waters (~10**?6 cm**2/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have Os/Ir ratios >/=1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (<10%) and Re (<0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most ~25% of the K-T impactor's Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the Os/Ir ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.

Influence of sediment acidification and water flow on sediment acceptance and dispersal of juvenile soft-shell clams (Mya arenaria L.)

Although ocean acidification is expected to reduce carbonate saturation and yield negative impacts on open-ocean calcifying organisms in the near future, acidification in coastal ecosystems may already be affecting these organisms. Few studies have addressed the effects of sedimentary saturation state on benthic invertebrates. Here, we investigate whether sedimentary aragonite saturation (Omega aragonite) and proton concentration ([H+]) affect burrowing and dispersal rates of juvenile soft-shell clams (Mya arenaria) in a laboratory flume experiment. Two size classes of juvenile clams (0.5-1.5 mm and 1.51-2.5 mm) were subjected to a range of sediment Omega aragonite and [H+] conditions within the range of typical estuarine sediments (Omega aragonite 0.21-1.87; pH 6.8-7.8; [H+] 1.58 × 10**-8-1.51 × 10**- 7) by the addition of varying amounts of CO2, while overlying water pH was kept constant ~ 7.8 (Omega aragonite ~ 1.97). There was a significant positive relationship between the percent of juvenile clams burrowed in still water and Omega aragonite and a significant negative relationship between burrowing and [H+]. Clams were subsequently exposed to one of two different flow conditions (flume; 11 cm/s and 23 cm/s) and there was a significant negative relationship between Omega aragonite and dispersal, regardless of clam size class and flow speed. No apparent relationship was evident between dispersal and [H+]. The results of this study suggest that sediment acidification may play an important role in soft-shell clam recruitment and dispersal. When assessing the impacts of open-ocean and coastal acidification on infaunal organisms, future studies should address the effects of sediment acidification to adequately understand how calcifying organisms may be affected by shifting pH conditions.

Chemical and isotopic composition of interstitial waters from the Kara Sea and Yenisey estuary

Processes of early sediment diagenesis, including chemical composition of interstitial waters, content of different sulfur compounds, and rates of sulfate reduction were investigated. Along a profile from the Yenisey River to the Kara Sea, sulfate reduction intensities were high (up to 1.5 µg S/kg/day) in the delta region and in its northern part. Intensities were comparable to those found in shallow-water sediments of the North Sea. In estuarine sediments, where different transformations were possible, lower rates of bacterial sulfate reduction were observed (0.03 to 0.06 µg S/kg/day). Annual production of reduced sulfur in sediments was 24 million tons, and only 0.5 million tons (2%) were deposited. Annual consumption of organic carbon during process of sulfate reduction in the Yenisey delta region was 17.6 million tons.

Seawater carbonate chemistry, calcification and shell size of hard clam Mercenaria mercenaria during experiments, 2011

Increasing atmospheric carbon dioxide threatens to decrease pH in the world's oceans. Coastal and estuarine calcifying organisms of significant ecological and economical importance are at risk; however, several biogeochemical processes drive pH in these habitats. In particular, coastal and estuarine sediments are frequently undersaturated with respect to calcium carbonate due to high rates of organic matter remineralization, even when overlying waters are saturated. As a result, the post-larval stages of infaunal marine bivalves must be able to deposit new shell material in conditions that are corrosive to shell. We measured calcification rates on the hard clam, Mercenaria spp.,in 5 post-larval size classes (0.39, 0.56, 0.78, 0.98, and 2.90 mm shell height) using the alkalinity anomaly method. Acidity of experimental water was controlled by bubbling with air-CO2 blends to obtain pH values of 8.02, 7.64, and 7.41, corresponding to pCO2 values of 424, 1120, and 1950 µatm. These pH values are typical of those found in many near-shore terrigenous marine sediments. Our results show that calcification rate decreased with lower pH in all 5 size classes measured. We also found a significant effect of size on calcification rate, with the smaller post-larval sizes unable to overcome dissolution pressure. Increased calcification rate with size allowed the larger sizes to overcome dissolution pressure and deposit new shell material under corrosive conditions. Size dependency of pH effects on calcification is likely due to organogenesis and developmental shifts in shell mineralogy occurring through the post-larval stage. Furthermore, we found significantly different calcification rates between the 2 sources of hard clams we used for these experiments, most likely due to genotypic differences. Our findings confirm the susceptibility of the early life stages of this important bivalve to decreasing pH and reveal mechanisms behind the increased mortality in post-larval juvenile hard clams related to dissolution pressure, that has been found in previous studies.

Speciation of metals in bottom sediments from the south Kara Sea and Ob and Yenisei estuarine zones

Speciation of Fe, Mn, Zn, Cu, Co, Ni, Cr, Pb, and Cd was studied in 52 samples of bottom sediments collected during Cruise 49 of the R/V "Dmitry Mendeleev" to the estuaries of the Ob and Yenisei rivers and to the southwest Kara Sea. Immediately after sampling the samples were subjected to on-board consecutive extraction to separate metal species according to their modes of occurrence in the sediments: (1) adsorbed, (2) amorphous Fe-Mn hydroxides and related metals, (3) organic + sulfide, and (4) residual, or lithogenic. Atomic absorption spectroscopy of the extracts was carried out at a stationary laboratory. Distribution of Fe, Zn, Cu, Co, Ni, Cr, Pb, and Cd species is characterized by predominance of lithogenic or geochemically inert modes (70-95% of bulk contents), in which the metals are bound in terrigenous and clastic mineral particles and organic detritus. About half of total Mn amount and 15-30% of Zn and Cu are contained in geochemically mobile modes. Spatiotemporal variations in proportions of the metal species in the surface layer of sediments along sub-meridional sections and through vertical sections of bottom sediment cores testify that Mn and, to a lesser extent, Cu are the most sensitive to changes in sedimentation environment. The role of their geochemically mobile species notably increases under reducing conditions.

Geochemical parameters of sediments and water of the Black Sea, data of Cruise 8 of R/V Vityaz-2

The book presents results of comprehensive geological investigations carried out during Cruise 8 of R/V "Vityaz-2" to the western part of the Black Sea in 1984. Systematic studies in the Black Sea during about hundred years have not weakened interest in the sea. Lithological and geochemical studies of sediments in estuarine areas of the Danube and the Kyzyl-Irmak rivers, as well as in adjacent parts of the deep sea and some other areas were the main aims of the cruise. Data on morphological structures of river fans, lithologic and chemical compositions of sediments in the fans and their areal distribution, forms of occurrence of chemical elements, role of organic matter and gases in sedimentation and diagenesis are given and discussed in the book.

Organic geochemistry of water and bottom sediments during a seasonal flood in 2006 in the North Dvina River estuary

Heavy contaminant load released into the Northern Dvina River during flooding increased the concentrations of aliphatic (AHC) and polcyclic aromatic (PAH) hydrocarbons in water and bottom sediments. The composition of hydrocarbons was different from that of the summer low flow season. The concentrations of dissolved and particulate AHC ranged from 12 to 106 and from 192 to 599 µg/l, respectively, and bottom sediments contained from 26.2 to 329 µg/g AHC and 4 to 1785 ng/g PAH. As the transformation of AHC occurred at low spring temperatures, the alkane composition was shown to be dominated by terrigenous compounds, whereas more stable PAH showed elevated contents of petrogenic and pyrogenic compounds. It was also shown that the Northern Dvina-Dvina Bay geochemical barrier prevents contaminant input into the White Sea, i.e., acts as a marginal filter.