Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

Sunken wood habitat for thiotrophic symbiosis in mangrove swamps

Large organic falls to the benthic environment, such as dead wood or whale bones, harbour organisms relying on sulfide-oxidizing symbionts. Nothing is known however, concerning sulfide enrichment at the wood surface and its relation to wood colonization by sulfide-oxidizing symbiotic organisms.In this study we combined in situ hydrogen sulfide and pH measurements on sunken wood, with associated fauna microscopy analyses in a tropical mangrove swamp. This shallow environment is known to harbour thiotrophic symbioses and is also abundantly supplied with sunken wood. A significant sulfide enrichment at the wood surface was revealed. A 72 h sequence of measurements emphasized the wide fluctuation of sulfide levels (0.1–>100 μM) over time with both a tidal influence and rapid fluctuations. Protozoans observed on the wood surface were similar to Zoothamnium niveum and to vorticellids. Our SEM observations revealed their association with ectosymbiotic bacteria, which are likely to be sulfide-oxidizers. These results support the idea that sunken wood surfaces constitute an environment suitable for sulfide-oxidizing symbioses.     

Experimental investigation of water impact on axisymmetric bodies

The results of an elaborate experimental investigation on bottom slamming of axisymmetric objects are presented. Drop tests have been performed on a hemisphere and two conical shapes with different deadrise angles. The test setup is designed so as to prevent small rotations of the test objects which cause scatter in the measurement data. The pressure distribution and evolution as well as the body motion parameters are measured during impact. By means of a high speed camera the water uprise is visualized and the wetting factor is determined for the cones. The results are compared with a three-dimensional asymptotic theory for axisymmetric rigid bodies with constant entry velocity. The ratio between the registered peak pressures and the asymptotic theory are in accordance with comparable experiments in the literature. The asymptotic theory, however, is found to be quite conservative, since the measured peak pressure levels appear to be approximately 50% to 75% of the theoretical levels.     

High-resolution record of tectonic and sedimentary processes in growth strata

Growth strata are used to determine the kinematics of synsedimentary structures such as faults. Classical methods of analysis such as thickness versus throw plot consider that the available space created by fault slip in the hanging wall of faults is instantaneously filled up by sediments. This has lead many previous works to identify a cyclic activity for growth faults. Here we perform a careful analysis of the variation of strata thicknesses on each side of a very well documented normal growth fault in the Niger delta. We show that these thickness variations are induced by the alternation of sedimentary processes during continuous fault slip. Suspended-load processes induce either uniform or slightly variable thickness of a large majority of mudstone layers. Bedload processes result in a preferential thickening of sand layers in the hanging wall. These high quality data thus provide strong grounds for doubting the polycyclic growth diagnosed for some faults at the scale of sedimentary cycles and supports the notion that fault displacement rates can be very well behaved. Our study emphasizes the important conclusion that stable fault growth, and related displacement rates, can appear to be punctuated when viewed at the scale of sedimentary cycles. It follows that care should be taken when attempting to derive displacement rates on temporal scales equivalent to those of alternating sedimentological cycles.     

Voracious planktonic hydroids: unexpected predatory impact on a coastal marine ecosystem

Hydroids are typically attached, benthic cnidarians that feed on a variety of small prey. During sampling on Georges Bank in spring 1994, we found huge numbers of hydroids suspended in the plankton. They fed on young stages of copepods that are an important prey for fish, as well as on young fish themselves. Two independent methods were used to estimate feeding rates of the hydroids; both indicate that the hydroids are capable of consuming from 50% to over 100% of the daily production of young copepods. These results suggest that hydroids can have a profound effect on the population dynamics of zooplankton and young fish on Georges Bank.     

A map series of the Southern East Pacific Rise and its flanks, 15° S to 19° S

Four large-scale bathymetric maps of the Southern East Pacific Rise and its flanks between 15° S and 19° S display many of the unique features of this superfast spreading environment including abundant seamounts (the Rano Rahi Field), axial discontinuities, discontinuity migration, and abyssal hill variation. Along with a summary of the regional geology, these maps will provide a valuable reference for other sea-going programs on-and off-axis in this area, including the Mantle ELectromagnetic and Tomography (MELT) experiment.     

Role of sea surface temperature and rainfall in determining the stock and fishery of the common octopus (Octopus vulgaris,Mollusca, Cephalopoda) in Tunisia

Octopus (Octopus vulgaris, Mollusca, Cephalopoda) is an important and valuable fishery resource on the eastern and southern coasts of Tunisia, but its landings are highly variable. This paper explores the effect of environment on octopus catch per unit effort (CPUE) during a 12‐year period, through correlation analyses and the incorporation into surplus production models of sea surface temperature (SST) and rainfall data collected during cold (January–May) and hot (August–October) seasons. CLIMPROD software was used to select the appropriate model and fit it to the fishery and environment data. In both seasons, SST significantly contributed to CPUE variability; fishery production was influenced positively by cold season SST but negatively by hot season SST. Due to a poor fit with cold season data, the impact of rainfall was analysed only for the hot season, during which it has a positive effect on production. Results are discussed in view of the life‐cycle of octopus and the dynamics of the Tunisian fishery. This first study of octopus variability in Tunisia highlights the necessity to incorporate environmental influence into stock assessment and management advice.     

Oxygen and organic carbon fluxes in sediments of the Bay of Biscay

The relationship between particulate organic carbon (POC) concentrations measured in modern sediment and fluxes of exported POC to the sediment surface needs to be understood in order to use POC content as a proxy of paleo-environmental conditions. The objective of our study was to compare POC concentrations, POC mineralization rates calculated from O₂ consumption and POC burial rates. Benthic O₂ distributions were determined in 58 fine-grained sediment cores collected at different periods at 14 stations in the southeastern part of the Bay of Biscay with depths ranging from 140 to 2800 m. Depth-dependent volume-specific oxygen consumption rates were used to assess rates of aerobic oxidation of organic matter (OM), assuming that O₂ consumption solely was related to heterotrophic activity at the sediment–water interface. Heterogeneity of benthic O₂ fluxes denoted changes in time and space of fresh organic material sedimentation. The most labile fraction of exported POC engendered a steep decrease in concentration in the upper 5 mm of vertical O₂ profiles. The rupture in the gradient of O₂ microprofile may be related to the bioturbation-induced mixing depth of fast-decaying carbon. Average diffusive O₂ fluxes showed that this fast-decaying OM flux was much higher than buried POC, although diffusive O₂ fluxes underestimated the total sediment oxygen demand, and thus the fast-decaying OM flux to the sediment surface. Sedimentary POC burial was calculated from sediment mass accumulation rate and the organic carbon content measured at the top of the sediment. The proportion of buried POC relative to total exported POC ranged at the most between 50% and 10%, depending on station location. Therefore, for a narrow geographic area like the Bay of Biscay, burial efficiency of POC was variable. A fraction of buried POC consisted of slow-decaying OM that was mineralized within the upper decimetres of sediment through oxic and anoxic processes. This fraction was deduced from the decrease with depth in POC concentration. At sites located below 500 m water depth, where the fast-decaying carbon did not reach the anoxic sediment, the slow-decaying pool may control the O₂ penetration depth. Only refractory organic material was fossilized in sedimentary records at locations where labile OM did not reach the anoxic portion of the sediment.     

Carbon fluxes through major phytoplankton groups during the spring bloom and post-bloom in the Northwestern Mediterranean Sea

The carbon flux through major phytoplankton groups, defined by their pigment markers, was estimated in two contrasting conditions of the Northwestern Mediterranean open ocean ecosystem: the spring bloom and post-bloom situations (hereafter Bloom and Post-bloom, respectively). During Bloom, surface chlorophyll a (Chl a) concentration was higher and dominated by diatoms (53% of Chl a), while during Post-bloom Synechococcus (42%) and Prymnesiophyceae (29%) became dominant. The seawater dilution technique, coupled to high pressure liquid chromatography (HPLC) analysis of pigments and flow cytometry (FCM), was used to estimate growth and grazing rates of major phytoplankton groups in surface waters. Estimated growth rates were corrected for photoacclimation based on FCM-detected changes in red fluorescence per cell. Given the 30% average decrease in the pigment content per cell between the beginning and the end of the incubations, overlooking photoacclimation would have resulted in a 0.40 d^?1 underestimation of phytoplankton growth rates. Corrected average growth rates (μ_o) were 0.90±0.20 (SD) and 0.40±0.14 d^?1 for Bloom and Post-bloom phytoplankton, respectively. Diatoms, Cryptophyceae and Synechococcus were identified as fast-growing groups and Prymnesiophyceae and Prasinophyceae as slow-growing groups across Bloom and Post-bloom conditions. The higher growth rate during Bloom was due to dominance of phytoplankton groups with higher growth rates than those dominating in Post-bloom. Average grazing rates (m) were 0.58±0.20 d^?1 (SD) and 0.31±0.07 d^?1. The proportion of phytoplankton growth consumed by microzooplankton grazing (m/μ_o) tended to be lower in Bloom (0.69±0.34) than in Post-bloom (0.80±0.08). The intensity of nutrient limitation experienced by phytoplankton indicated by μ_o/μ_n (where μ_n is the nutrient-amended growth rate), was similar during Bloom (0.78) and Post-bloom (0.73). Primary production from surface water (PP) was estimated with ¹⁴C incubations. A combination of PP and Chl a synthesis rate yielded C/Chl a ratios of 34±21 and 168±75 (g:g) for Bloom and Post-bloom, respectively. Transformation of group-specific Chl a fluxes into carbon equivalents confirmed the dominant role of diatoms during Bloom and Synechococcus and Prymnesiophyceae during Post-bloom.     

Diagnosis of trace metal contamination in sediments: the example of Ensenada and El Sauzal, two harbors in Baja California, Mexico

Total metal concentrations in sediments from within Ensenada and El Sauzal Harbors are generally higher than at the mouths. Grain-size analyses suggested that this enrichment could be due to the presence of fine-grained sediments in the inner part of the harbors rather than to anthropogenic perturbations. The (Me/Al)(sample) ratios for Pb, Co, Ni and Fe were significantly higher for Ensenada Harbor relative to El Sauzal Harbor, whereas the ratios for Cd, Mn, Zn and Cu were statistically equivalent for both harbors. Calculated enrichment factors [EF(Me)=(Me/Al)(sample)/(Me/Al)(shale)] indicated that the metals showing slight enrichment were those associated with anthropogenic contamination (Pb, Zn), or probably related to primary productivity in the water column (Cd, Co). The levels of most of the metals were not greatly enriched, a consideration that is of the utmost importance when contamination issues are at stake.