Mercury speciation in surface and deep waters of the Mediterranean Sea

Mercury speciation and its distribution in surface and deep waters of the Mediterranean Sea were studied during two oceanographic cruises on board the Italian research vessel URANIA in summer 2003 and spring 2004 as part of the Med Oceaneor and MERCYMS projects. The study included deep water profiles of dissolved gaseous Hg (DGM), reactive Hg (RHg), total Hg (THg), monomethyl Hg (MeHg) and dimethyl Hg (DMeHg) in open ocean waters. Average concentrations of measured Hg species were characterized by seasonal and spatial variations. Overall average THg concentrations ranged between 0.41 and 2.65 pM (1.32 ± 0.48 pM) and were comparable to those obtained in previous studies of the Mediterranean Sea. A significant fraction of Hg was present as “reactive” Hg (average 0.33 ± 0.32 pM). Dissolved gaseous Hg (DGM), which consists mainly of Hg⁰, represents a considerable proportion of THg (average 20%, 0.23 ± 0.11 pM). The portion of DGM typically increased towards the bottom, especially in areas with strong tectonic activity (Alboran Sea, Strait of Sicily, Tyrrhenian Sea), indicating its geotectonic origin. No dimethyl Hg was found in surface waters down to the depth of 40 m. Below this depth, its average concentration was 2.67 ± 2.9 fM. Dissolved fractions of total Hg and MeHg were measured in filtered water samples and were 0.68 ± 0.43 pM and 0.29 ± 0.17 pM for THg and MeHg respectively. The fraction of Hg as MeHg was in average 43%, which is relatively high compared to other ocean environments. The concentrations reported in this study are among the lowest found in marine environments and the quality of analytical methods are of key importance. Speciation of Hg in sea water is of crucial importance as THg concentrations alone do not give adequate data for understanding Hg sources and cycling in marine environments. For example, photoinduced transformations are important for the presence of reactive and elemental mercury in the surface layers, biologically mediated reactions are important for the production/degradation of MeHg and DGM in the photic zones of the water column, and the data for DGM in deep sea indicate the natural sources of Hg in geotectonicaly active areas of the Mediterranean Sea.     

Contaminant concentrations and toxicity of sea-surface microlayer near Los Angeles, California

Sea-surface microlayer samples were collected from six nearshore areas receiving different amounts of anthropogenic inputs. The samples were analyzed for selected trace metals, chlorinated hydrocarbons, and polycyclic aromatic hydrocarbons. The relative toxicities of the samples were determined with fish embryo bioassays.Contaminant concentrations generally increased from offshore to the inshore stations. Contaminant concentrations were several orders of magnitude higher in microlayer samples from the highly industrialized Los Angeles and Long Beach harbors compared to samples from a site 15km offshore. Microlayer samples from the inshore stations were significantly more toxic, and induced significantly more developmental abnormalities and chromosome aberrations, than samples from the offshore stations.     

Trace metals in the Western Pacific: temporal and spatial variability in the concentrations of Cd, Cu, Mn and Ni

Profiles of total dissolvable Cd, Cu, Mn and Ni are reported for samples collected from the southwest Pacific in 1989, from the western equatorial Pacific along 155°E at 5°S, 0° and 5°N in 1990 and 1993, and along the equator from 143°E to 152°E and in the Bismarck Sea in 1997 and 2000. Profiles of Cd along 155°E in 1990 and along the equator were essentially the same but, in 1993, Cd values at 5°N were higher by a factor of about 1.5–2 than at 5°S over the depth range 500–1500 m. Similar, but less pronounced, differences were observed for PO₄ and Ni. Cd and Ni were both strongly correlated with PO₄, and an even stronger correlation was found between Ni and Cd. The concentration of Ni did not fall below ≈2 nmolkg⁻¹, even in the nitrate-depleted waters of the western equatorial Pacific, where primary production is strongly dependent on recycled nitrogen (mainly ammonia and urea). It is proposed that this residual Ni is not bioavailable and that Ni could be biolimiting, since the metabolism of urea requires the nickel-containing enzyme urease. The impact of the Sepik River on Cd, Cu and Ni concentrations was small but elevated concentrations of Mn were observed near the Sepik River and close to the coast suggesting that the rivers and sediments on the north coast of New Guinea are a significant local source of Mn to the Bismarck Sea. Simple mass balance calculations show that the elevated levels of Mn observed in the Equatorial Undercurrent cannot be due to input from the rivers of New Guinea and they were attributed to the trapping of particulate matter due to strong current shear. A strong hydrothermal source of Mn was observed in the central Bismarck Sea.     

Evaluation of bending moments and shear forces at unit connections of very large floating structures using hydroelastic and rigid body analyses

This paper investigates the characteristics of bending moments, shear forces and stresses at unit connections of very large floating structures (VLFS) under wave loads. The responses of VLFS are calculated by solving multi-body motion equation considering hydroelasticity and connection stiffness. Hydroelastic responses are calculated by the direct method. Higher-order boundary element method (HOBEM) is used for fluid analysis and finite element method (FEM) is introduced for structural analysis. The equation of motion is modified to describe the unit connections by employing spring elements. Bending moments and shear forces at the connections are obtained from the dynamic equilibrium condition for pressures and inertia forces. Two types of VLFS units such as tandem arranged units and side-by-side arranged units are considered in the numerical examples. The influences of connection stiffness, wave frequency and heading angle on responses of VLFS are investigated through the numerical examples. Rigid body analysis along with hydroelastic analysis is also carried out in the numerical analysis and comparison of those two approaches is discussed.     

Phytoplankton and iron: validation of a global three-dimensional ocean biogeochemical model

The JGOFS program and NASA ocean-color satellites have provided a wealth of data that can be used to test and validate models of ocean biogeochemistry. A coupled three-dimensional general circulation, biogeochemical, and radiative model of the global oceans was validated using these in situ data sources and satellite data sets. Biogeochemical processes in the model were determined from the influences of circulation and turbulence dynamics, irradiance availability, and the interactions among four phytoplankton functional groups (diatoms, chlorophytes, cyanobacteria, and coccolithophores) and four nutrients (nitrate, ammonium, silica, and dissolved iron).Annual mean log-transformed dissolved iron concentrations in the model were statistically positively correlated on basin scale with observations (P<0.05) over the eight (out of 12) major oceanographic basins where data were available. The model tended to overestimate in situ observations, except in the Antarctic where a large underestimate occurred. Inadequate scavenging and excessive remineralization and/or regeneration were possible reasons for the overestimation.Basin scale model chlorophyll seasonal distributions were positively correlated with SeaWiFS chlorophyll in each of the 12 oceanographic basins (P<0.05). The global mean difference was 3.9% (model higher than SeaWiFS).The four phytoplankton groups were initialized as homogeneous and equal distributions throughout the model domain. After 26 years of simulation, they arrived at reasonable distributions throughout the global oceans: diatoms predominated high latitudes, coastal, and equatorial upwelling areas, cyanobacteria predominated the mid-ocean gyres, and chlorophytes and coccolithophores represented transitional assemblages. Seasonal patterns exhibited a range of relative responses: from a seasonal succession in the North Atlantic with coccolithophores replacing diatoms as the dominant group in mid-summer, to successional patterns with cyanobacteria replacing diatoms in mid-summer in the central North Pacific. Diatoms were associated with regions where nutrient availability was high. Cyanobacteria predominated in quiescent regions with low nutrients.While the overall patterns of phytoplankton functional group distributions exhibited broad qualitative agreement with in situ data, quantitative comparisons were mixed. Three of the four phytoplankton groups exhibited statistically significant correspondence across basins. Diatoms did not. Some basins exhibited excellent correspondence, while most showed moderate agreement, with two functional groups in agreement with data and the other two in disagreement. The results are encouraging for a first attempt at simulating functional groups in a global coupled three-dimensional model but many issues remain.     

Remote sensing and surface POC concentration in the South Atlantic

Several SeaWiFS products have been compared with shipboard data to assess the possibility of using remote sensing to estimate particulate organic carbon (POC) concentration in surface waters. Transmissometer data were collected during six South Atlantic Ventilation Experiment (SAVE) hydrographic expeditions conducted between November 1987 and March 1989 from R/V Knorr, and Melville. A total of 361 beam attenuation profiles were made with a SeaTech transmissometer interfaced with a CTD/rosette. In order to calculate the POC concentration from transmissometer profiles, a regression between beam attenuation and POC for open Atlantic Ocean waters derived from our research in the North Atlantic (North Atlantic Bloom Experiment, NABE) and enhanced by data from the Bermuda Atlantic Time Series Station (BATS) was applied. The profiles were processed and examined as vertical sections of the surface 250 m. The data were collected in two successive years, during the same season, which allowed us to compile a combined data set over the austral summer for examination. Beam attenuation/POC concentrations were integrated down to one attenuation depth with the intent of making comparisons with satellite optical data. No satellite optical data were available for 1987–1989, so the only option was to compare our integrated data with SeaWiFS-derived variables from later years averaged over the same season as SAVE data. Analysis of four SeaWiFS products acquired from 1997 to 2002 demonstrated very low variations from year to year for seasonally averaged data, suggesting that making comparisons of the beam attenuation/POC fields with averaged satellite optical products from later years is a valid (though not optimal) approach for this area. The highest correlation between beam attenuation/POC concentration and remotely derived products was found with normalized water-leaving radiance at 555 nm. Other SeaWiFS-derived variables—chlorophyll concentration, diffuse attenuation coefficient at 490 nm and integral chlorophyll (integrated over one attenuation depth)—were also compared but showed a slightly less satisfactory correlation.