Evaluation of ferrous and ferric Mössbauer fractions

The Mössbauer fractions f for various ferrous- and/or ferric-containing oxides and oxyhydroxides, silicates and carbonates were evaluated from the experimental temperature dependence of their center shifts, using the Debye approximation for the second-order Doppler shift. It is concluded that ferrous ions exhibit a lower fraction as compared to ferric ions. Using standard mixtures of -Fe₂O₃ with selected Fe²⁺ or Fe³⁺ compounds, it is found that the calculated Fe³⁺ f values are somewhat overestimated with respect to those of Fe²⁺. Possible explanations for this shortcoming are discussed and it is suggested that a different temperature dependence of the intrinsic isomer shift is the most likely reason. This suggestion is corroborated by analyses of hematite and hedenbergite data which are available for temperatures up to 900 K and 800 K respectively.     

Benthic fluxes of mercury species in a lagoon environment (Grado Lagoon,Northern Adriatic Sea,Italy)

The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g⁻¹, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g⁻¹) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L⁻¹, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m⁻² day⁻¹) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m⁻² day⁻¹) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m⁻² day⁻¹ at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O₂ and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O₂ depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.     

The Messinian Sicilian stratigraphy revisited: new insights for the Messinian salinity crisis

Controversies around the Messinian salinity crisis (MSC) are because of the difficulties in establishing genetic and stratigraphic relationships between its deep and shallow‐water record. Actually, the Sicilian foreland basin shows both shallow and deep‐water Messinian records, thus offering the chance to reconstruct comprehensive MSC scenarios. The Lower Gypsum of Sicily comprises primary and resedimented evaporites separated in space and time by the intra‐Messinian unconformity. A composite unit including halite, resedimented gypsum and Calcare di Base accumulated between 5.6 and 5.55 Ma in the main depocentres; it records the acme of the Messinian Salinity Crisis during a tectonic phase coupled with sea‐level falls at glacials TG14‐TG12. These deposits fully post‐date primary gypsum, which precipitated in shallow‐water wedge‐top and foreland ramp basins between 5.96 and 5.6 Ma. This new stratigraphic framework results in a three‐stage MSC scenario characterized by different primary evaporite associations: selenite in the first and third stages, carbonate, halite and potash salt in the second one associated with hybrid resedimented evaporites.     

Total content and chemical speciation of arsenic in the polychaete Sabella spallanzanii

An unusual feature has been observed in polychaetes regarding their capacity to accumulate high levels of relatively toxic forms of arsenic in specific tissues. Basal levels of arsenic and distribution of its compounds were investigated in tissues of the Mediterranean polychaete Sabella spallanzanii. Particularly high concentrations were measured in the branchial crown (1036+/-136 microg/g d.w.) and chemical speciation revealed that the predominant form was the relatively toxic dimethylarsinate (DMA). These data suggest a potential role of As as anti-predatory strategy in polychaetes.     

Steady-state analysis of undersea cables

A numerical solution and computer program developed to analyse undersea flexible cable problems is presented. The cable is subject to hydrodynamic loads from a surrounding fluid medium. The object is to determine the cable profile and tensile forces developed. The cable equations and boundary conditions result in a classical two-point boundary value problem. An iteration ‘shooting method’ is used for solution. The program has been written to analyse a class of towing and anchoring problems. However the analysis is general and applicable to most steady-state cable problems.     

南海尖峰海山多金属结壳地球化学

南海尖峰海山多金属结壳富含30多种元素,其锰铁矿物主要由钡镁锰矿,δ-MnO_2和FeOOH·xH_2O组成。与其它海区的结壳相比,尖峰海山结壳富含Cu、Ni、Ba、Zn、Pb等元素,而Co、Ti、稀土元素(REE)、Sr等元素相对较贫。研究表明,HREE亏损,具明显的Ce正异常,较明显的Tb正异常和Yb负异常。这是氧化弱碱性海洋环境所致。结壳是水成作用的产物,它的形成受南海独特的古海洋环境所控制,海底火山热液作用,可能也是影响因素之一。     

Sensitivity to stress of the estuarine bivalve Macoma balthica from areas between the Netherlands and its southern limits (Gironde)

Variation in the sensitivity to stress of Macoma balthica was measured in several French and Dutch estuaries. For adult and juvenile Macoma balthica exposed to copper under conditions of starvation, differences in mortality rate, condition, glycogen, burrowing rate and copper content were assessed. No significant differences were observed between adults and juveniles; the influence of treatment and origin was always evident. Animals from the most southern estuaries, Loire and Gironde, near to the species's southern limit of distribution, showed, in the field, the strongest deviations for the ecophysiological traits measured, and were in the experiments the most sensitive to stress.     

Factors involved in growth plasticity of cockles Cerastoderma edule (L.), identified by field survey and transplant experiments

In Arcachon Bay, a macrotidal coastal lagoon in southwest France, growth rates of cockles Cerastoderma edule (L.) differ greatly between locations. Sampling of populations at different tidal levels showed that the mean shell length was significantly and positively correlated with immersion time, whereas no correlation was found with population density and microphytobenthos biomass. Transplants of cockles between two intertidal sites were used to examine the relative importance of habitat and site of origin for growth rate and condition index. Artifacts due to manipulation were assessed, i.e. the impact of enclosures on growth, conditon index and mortality. During a 5-mo reciprocal transplant experiment, growth rates of the transplanted cockles and the cockles already present were similar, whereas the sites of origin did not affect growth rate. Condition index, however, displayed significant differences in relation to both transplant and origin sites. During a further 6-mo experiment in which cockles were transplanted from one site to four new sites, growth was mainly influenced by tidal level. These results indicate that net growth started when cockles were immersed 30% of the time. It is concluded that, on the scale of Arcachon Bay (156 km²), differences in growth and condition between cockle populations are largely phenotypic. Tidal level (i.e. food supply and emersion stress) accounts for most of these differences, but the existence of genetically or physiologically different populations cannot be excluded.