Voltammetric estimation of iron(III) thermodynamic stability constants for catecholate siderophores isolated from marine bacteria and cyanobacteria

Thermodynamic stability constants have been estimated for the complexation of iron(III) with catecholate-type siderophores isolated from the marine bacterium Alteromonas luteoviolacea and from the marine cyanobacterium Synechococcus sp. PCC 7002. Stability constants were determined utilizing the “chelate scale” of Taylor et al. (1994). The scale is based upon a linear relationship between the reduction potentials and the pH-independent thermodynamic stability constants for known iron(III) complexes. Log K values for the alterobactin B ferric iron complex are 43.6 ± 1.5 at pH 8.2 and 37.6 ± 1.2 at pH 6, consistent with a shift from bis-catecholate to monosalicylate/monocatecholate iron coordination with decreasing pH. Synechococcus isolates PCC 7002 Nos. 1 and 3 formed iron(III) complexes with stability constants of approximately 38.1 ± 1.2 and 42.3 ± 1.5, respectively. The binding strengths of the iron(III) complexes examined in this study are quite high, suggesting that catecholate siderophores may play a role in the solubilization and biological uptake of iron in the marine environment.     

Annual Anthropogenic Carbon Transport into the North Pacific Intermediate Water through the Kuroshio/Oyashio Interfrontal Zone: An Estimation from CFCs Distribution

Vertical distribution of anthropogenic carbon content of the water (exDIC) in the Oyashio area just outside of the Kuroshio/Oyashio Interfrontal Zone (K/O Zone) was estimated by the simple 1-D advection-diffusion model calibrated by the distribution of chlorofluorocarbons (CFCs). The average concentration of exDIC for = 26.60–27.00 is multiplied by the volume transport of Oyashio water into the North Pacific Intermediate Water (NPIW) to estimate the annual transport of exDIC into NPIW through K/O Zone. The estimated transport of exDIC was 0.018–0.020 GtC/y, which corresponds to 15% of the whole total exDIC accumulation in the temperate North Pacific. A simple assessment using the NPIW 1-box model indicates that the current study explains at least 70% of the total annual transport of exDIC into NPIW, and that small exDIC sources for NPIW still exists in addition to K/O Zone.     

Trophic accumulation and depuration of mercury by blue crabs (Callinectes sapidus) and pink shrimp (Penaeus duorarum)

Mercury concentrations in blue crabs (Callinectes sapidus) collected from an area of mercury-contaminated sediments in Lavaca Bay, TX, USA, are more than an order of magnitude greater than concentrations in penaeid shrimp from the same area. Laboratory feeding experiments using mercury-contaminated fish as food showed that both blue crabs and pink shrimp (Penaeus duorarum) could accumulate mercury concentrations comparable to those in their food in 28 days. Calculated mercury assimilation efficiencies averaged 76% for blue crabs and 72% for pink shrimp. Significant depuration of mercury by blue crabs was not observed during a subsequent 28-day period, but pink shrimp lost mercury at a rate of about 0.012 day-1. Model calculations predict biomagnification factors of mercury of about two to three at steady state for both species. The large difference in observed concentrations of mercury in field-collected blue crabs and penaeid shrimp does not result from differences in efficiency of mercury assimilation from their food or from differences in excretion rates. It is more likely the result of differences in residence times in the contaminated area and of differences in feeding habits.     

Long-term recovery of a Louisiana brackish marsh plant community from oil-spill impact: vegetation response and mitigating effects of marsh surface elevation

Oil spills can have significant, short-term, negative impacts on coastal marshes, but the long-term effects and eventual recovery are not well documented, particularly in brackish marshes. The goals of this investigation were to: (1) document the long-term recovery of a Louisiana brackish marsh plant community impacted by a 1985 oil spill; (2) separate the effect of the oil spill on marsh deterioration from ambient rates of marsh deterioration; and (3) assess the relative importance of residual oil in the sediment and decreased marsh surface elevation in the failure of certain areas to recover. A total of 68 permanent plots previously established in 1985 were re-surveyed for plant and soil recovery in the fall of 1989. Although substantial (and near total) vegetative recovery was evident by significant increases in live and total vegetative cover, many of the plots that were initially heavily impacted by oil still displayed elevated levels of total saturated hydrocarbons in the soil. August 1990 measurements of plant photosynthetic response and edaphic variables revealed no significant differences between control plots and plots heavily impacted by oil that displayed vegetative regrowth. Rates of wetland land loss in the oiled marsh during an 8-year period that bracketed the time of the spill were within the historical range measured for this site and similar to the land loss rates of adjacent reference marshes. Results from a manipulative field transplant experiment indicated that the long-term failure of certain small areas to revegetate was primarily due to a decrease of marsh surface elevation (increased flooding stress), not a residual oil effect.     

Etiologies, observations and reporting of estuarine finfish lesions.

Lesions in estuarine finfish are associated with a variety of organisms including parasites and bacterial, viral, and fungal infectious agents. In addition, trauma, suboptimal water quality, and other abiotic stress factors may result in the loss of homeostasis. We have observed solitary ulcerative lesions on menhaden sampled from the Chesapeake Bay, Maryland, the Pimlico River, North Carolina, and the St. Johns River, Florida. Histologically, the lesions demonstrated a marked chronic inflammatory infiltrate and granulomas in response to fungal hyphae throughout large areas of exposed necrotic muscle. Gram-negative rod-shaped bacteria were also observed in the lesions, a common finding in ulcers of aquatic organisms. Similar observations in menhaden and other species have been described previously in the literature as ulcerative mycosis, mycotic granulomatosis, red spot disease, and epizootic ulcerative syndrome. Despite the many different known causes of fish lesions, the popular press and the scientific literature have recently emphasized Pfiesteria piscicida and other Pfiesteria-like dinoflagellates (and their bioactive compounds) as the primary causative agent for finfish lesions, particularly mycotic granulomatous ulcers in Atlantic menhaden. While some laboratory data suggest that Pfiesteria may play a role in field-observed lesions, much more cause-and-effect evidence is needed to determine the importance of other risk factors, both alone or and in combination with Pfiesteria. In order to better understand the etiology of lesion initiation and progression in estuarine finfish, accurate assessments of environmental conditions collected on appropriate temporal and spatial scales, and fish morphological indicators consistent with gross and histological pathologic terminology, should be used for reporting fish lesion observations and kills. Further, this outlook will help to avoid bias and may foster a broader perspective for examining the health of estuarine systems in general.     

Video cathodoluminescence microscopy of diagenetic cements and its applications

Diagenetic studies of sedimentary rocks using cold cathodoluminescence (CL) microscopy have been severely limited because of the very low intensity of visible luminescent emissions, which required long photographic exposure times, and because of the difficulty in obtaining quantitative data from CL observations. The solution to this problem is to fit the microscope with a high-sensitivity digital colour video camera linked to a computer with image enhancement and image analysis software. The new technique described in this paper:

• produces digital CL images of consistent high quality, both quickly and cheaply;

• controls the capture and editing of CL images, to reveal detailed textural information even from minerals exhibiting low level luminescence such as quartz;

• acquires quantitative information on pore systems and the abundance of cement zones from CL images.

Examples are presented to demonstrate the high quality of images produced in this way and the range of uses to which the new technique can be applied. The ability to image exactly the same field of view in both plane polarised light and CL is a particular advantage. Image analysis techniques have been developed to give a statistical characterisation of both pore systems and cement phases that infill them. The abundance of contrasting cement zones seen in CL can be measured and the abundance of cement phases can be mapped across a reservoir. The history of porosity occlusion can be reconstructed quantitatively and integrated with burial history and hydrocarbon migration. Porosity can be measured accurately and, since the technique obtains data on pore geometry as well as abundance, the pore system can be characterised by pore size distributions and pseudo-capillary pressure curves. This also opens the possibility of estimating permeability from thin sections.     

Trace metal composition of colloidal organic material in marine environments

Marine colloidal material (1 kDa–0.2 μm) was isolated by cross-flow ultrafiltration followed by diafiltration and freeze-drying from surface waters of the Gulf of Mexico and the Middle Atlantic Bight (MAB), as well as from estuarine waters of Galveston Bay. Elemental characterization of isolated colloidal material included organic carbon (OC) and selected trace metal (Cu, Pb, Zn, Cd, Co, Ni, Cr, Be, Fe, Al, Mn, V, Ba, and Ti) determinations. It was found that levels of these metals in marine colloids ranged from <0.1 to 50 μg/g colloidal matter, except for Fe which generally had a concentration >120 μg/g. Most metals (Cu, Pb, Zn, Ni, Al, Mn, V, and Ti) had an average concentration >1 μg/g while concentrations of Cd, Co and Be were usually <1 μg/g. Metal concentrations (μg/g) in isolated colloids were, in general, higher in Galveston Bay than in the Gulf of Mexico, suggesting either high abundance of trace metals in estuarine waters or differences in organic matter composition. Higher colloidal metal concentrations in the MAB than in the Gulf of Mexico might be due to higher terrestrial inputs in the MAB. Colloidal metal concentrations (μg/g) were generally lower than those in average soils, continental crust and suspended particles. However, metal/aluminum ratios (Me/Al) in isolated marine colloids were significantly higher than those for average soils and continental crust. Most importantly, colloids had a metal composition and metal/OC ratio (Me/C) similar to humic substances and marine plankton, suggesting that marine colloids largely originate from planktonic sources and are composed of predominately organic components. The Me/C ratios of Galveston Bay colloids followed the sequence of Cu>Ni, Cr, Zn>Mn>Co>Pb, Cd, which is similar to the Irving–Williams order except for Mn, suggesting that the interaction of metals with marine colloids is determined by the affinity of metals for specific organic ligands.     

An inventory of factors that affect polysaccharide production by Phaeocystis globosa

Phaeocystis material contains polysaccharides that are built from at least eight different monosaccharides. Differences have been reported between the carbohydrate composition of different Phaeocystis species, and also between samples taken from Phaeocystis globosa blooms in different areas. In order to elucidate factors that could play a role in determining variation in carbohydrate composition and production, a number of Phaeocystis globosa strains were studied under laboratory conditions. Although there was a clear distinction of a northern and a southern cluster in the Phaeocystis globosa strains based on RAPD analysis, the differences in the composition of the mucopolysaccharides were relatively small. The contribution of glucose, however, ranged from 7–85% of total sugars. A strain that was cultured in seawaters of diverse origin produced polysaccharides of a different composition, suggesting the effect of environmental factors. The presence of bacteria affected neither the amount, nor the composition of the carbohydrates that were produced by Phaeocystis globosa. Glucose is part of both the intracellular polysaccharide pool and of the mucopolysaccharides in the colony matrix. Using specific digestion of the intracellular chrysolaminaran by laminarinase, the distribution of polysaccharides over different pools could be assessed. During growth of an axenic, mucus-producing strain, the portion of glucose present as chrysolaminaran appeared to increase. The polyglucose that was not digested by laminarinase remains unidentified. This study shows that environmental factors rather than strain differences determine differences in the sugar composition of Phaeocystis globosa, especially with respect to the glucose content of the material. A difference in the contribution of glucose could be correlated to the portion of cells in the culture that are not in the colonies. Our study emphasises that for studying polysaccharide dynamics in Phaeocystis globosa it is important to be able to discriminate between the different polysaccharide pools. Preliminary results of an enzymatic approach were promising