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.     

Incorporating Māori values into land management decision tools

ABSTRACT

Environmental sustainability and the long-term wellbeing of Māori (the indigenous people of New Zealand) are interdependent and degradation of landscapes risks the progressive degradation of Māori wellbeing. The present study developed an analysis framework based on Ki Uta Ki Tai (holistic-mountains to the sea- management philosophy advocated by Ngāi Tahu) for exploring relationships between landcover and Māori values to enable predictions of cultural values through space and time. We used this framework to predict how two Māori values (Overall Health and Cultural Land Use) have been altered as a result of landcover change between 2001–2012 in three Canterbury catchments. The area of native vegetation declined while exotic pasture increased between 2001–2012, and there were corresponding declines in both cultural health scores. These results suggest that the change in landcover has reduced the ability of the landscape to support Māori values. This framework for assessing changes in Māori values with respect to changing environmental conditions may identify opportunities for Māori to better engage in land use management decisions.     

The impact of wave loads and pore-water pressure generation on initiation of sediment transport

The build-up of pore-water pressure by waves can lead to sediment liquefaction and subsequent transport by traction currents. This process was investigated by measuring pore-water pressures both in a field experiment and laboratory wave tank tests. Liquefaction was observed in the wave tank tests. The results suggest that sand is less susceptible than silts to wave-induced liquefaction because of the tendency to partially dissipate pore-water pressures. However, previous studies have determined that pore-water pressures must approach liquefaction before current velocities necessary to initiate transport are reduced. Once liquefaction has occurred more sediment can be transported.     

Profiles of dissolved and acid-leachable selenium in a sediment core from the lower St. Lawrence estuary

Concentrations of Se in the pore-water and in the solid phase, and the concentrations of other diagenetic constituents (Fe, Mn, phosphate, ammonium and I) in pore-water, were determined in a sediment core from a 350-m deep station in the lower St. Lawrence Estuary. The concentration of dissolved Se in pore-water was 2.1 nmol kg⁻¹ at the surface of the core, increasing to a maximum of 7.6 nmol kg⁻¹ at a depth of 12 cm, and thereafter decreasing gradually with depth. This profile is similar to the profiles of Fe and phosphate, whose concentration maxima occur around 10 cm. The concentration of total sedimentary Se remained almost constant with depth (≈ 0.75 mg kg⁻¹); however, a significant enrichment of oxalate-leachable Se was observed in the top 2 cm. The sedimentary cycling of Se appears to be closely related to that of Fe: adsorption of Se onto Fe oxyhydroxide at or near the sediment-water interface, release of the adsorbed Se by the reduction of Fe oxyhydroxide, and removal by formation of ferroselite (FeSe₂) at depth. The pore-water flux of Se was estimated by two different methods, firstly from the pore-water gradient, and secondly by applying a box model to the oxalate-leachable solid-phase Se data. The methods agree well both giving values for the flux of 0.11 nmol cm⁻² year⁻¹. This agreement suggests that the loss of labile Se in the sediment is balanced by the upward flux of dissolved Se.     

Storms and shoreline retreat in the southern Gulf of St. Lawrence

Storms play a major role in shoreline recession on transgressive coasts. In the southern Gulf of St. Lawrence (GSL), southeastern Canada, long-term relative sea-level rise off the North Shore of Prince Edward Island has averaged 0.3 m/century over the past 6000 years (>0.2 m/century over 2000 years). This has driven long-term coastal retreat at mean rates >0.5 m/a but the variance and details of coastal profile response remain poorly understood. Despite extensive sandy shores, sediment supply is limited and sand is transferred landward into multidecadal to century-scale storage in coastal dunes, barrier washover deposits, and flood-tidal delta sinks. Charlottetown tide-gauge records show mean relative sea-level rise of 3.2 mm/a (0.32 m/century) since 1911. A further rise of 0.7±0.4 m is projected over the next 100 years. When differenced from tidal predictions, the water-level data provide a 90-year record of storm-surge occurrence. Combined with wind, wave hindcast, and sea-ice data, this provides a catalogue of potentially significant coastal storms. We also document coastal impacts from three recent storms of great severity in January and October 2000 and November 2001. Digital photogrammetry (1935–1990) and shore-zone surveys (1989–2001) show large spatial and temporal variance in coastal recession rates, weakly correlated with the storm record, in part because of wave suppression or coastal protection by sea ice. Large storms cause rapid erosion from which recovery depends in part on local sand supply, but barrier volume may be conserved by washover deposition. Barrier shores with dunes show high longshore and interdecadal variance, with extensive multidecadal healing of former inlet and overwash gaps. This reflects recovery from an episode of widespread overwash prior to 1935, possibly initiated by intense storms or groups of storms in the latter half of the 19th century. With evidence from the storms of 2000–2001, this points to the importance of storm clustering on scales of weeks to years in determining erosion vulnerability, as well as the need for a long-term, large-scale perspective in assessing coastal stability. The expected acceleration in relative sea-level rise, together with projections of increasing storm intensity and greatly diminished winter ice cover in the southern GSL, implies a significant increase in coastal erosion hazards in future.     

The toxicity of one-hour silver exposures to early-life stages of the surf Spisula solidissima (Dillwyn)

Early life stages of Spisula solidissima (1-, 4-, 8- and 12-h post-fertilization) were exposed to various concentrations of silver in solution (0, 4, 8, 24, 44, 124 and 278 μg liter^?1) for 1 h. An additional group of 1-h post-fertilized eggs was treated with 0, 4, 11 and 24 μg liter^?1 silver continuously for 48h. Results indicate that younger embryos are more susceptible to Ag. Exposure of one-hour-old embryos to silver for only 1 h gives results similar to a continuous 48-h exposure to the same concentration of Ag. The calculated EC₅₀ for 48-h continuously exposed embryos was similar to the EC₅₀ for 1-h post-fertilized embryos that were exposed to silver for only 1 h.     

Mean flow and variability in the southwestern East Sea

The Ulleung Basin is one of three deep basins that are contained within the East/Japan Sea. Current meter moorings have been maintained in this basin beginning in 1996. The data from these moorings are used to investigate the mean circulation pattern, variability of deep flows, and volume transports of major water masses in the Ulleung Basin with supporting hydrographic data and help from a high-resolution numerical model. The bottom water within the Ulleung Basin, which must enter through a constricted passage from the north, is found to circulate cyclonically—a pattern that seems prevalent throughout the East Sea. A strong current of about 6 cms⁻¹ on average flows southward over the continental slope off the Korean coast underlying the northward East Korean Warm Current as part of the mean abyssal cyclonic circulation. Volume transports of the northward East Korean Warm Current, and southward flowing East Sea Intermediate Water and East Sea Proper Water are estimated to be 1.4 Sv (1 Sv=10⁻⁶ m³ s⁻¹), 0.8 Sv, and 3.0–4.0 Sv, respectively. Deep flow variability involves a wide range of time scales with no apparent seasonal variations, whereas the deep currents in the northern East Sea are known to be strongly seasonal.     

Th sorption and export models in the water column: A review

Over the past few decades, the radioisotope pair of ²³⁸U / ²³⁴Th has been widely and increasingly used to describe particle dynamics and particle export fluxes in a variety of aquatic systems. The present paper is one of five review articles dedicated to ²³⁴Th. It is focused on the models associated with ²³⁴Th whereas the companion papers (same issue) are focused on present and future methodologies and techniques (Rutgers van der Loeff et al.), C / ²³⁴Th ratios (Buesseler et al.), ²³⁴Th speciation (Santschi et al.) and present and future applications of ²³⁴Th [Waples, J.T., Benitez-Nelson, C.R., Savoye, N., Rutgers van der Loeff, M., Baskaran, M., Gustafsson, Ö., this issue. An Introduction to the application and future use of ²³⁴Th in aquatic systems. Marine Chemistry, FATE special issue]. In this paper, we review current ²³⁴Th scavenging models and discuss the relative importance of the non-steady state and physical terms associated with the most commonly used model to estimate ²³⁴Th flux. Based on this discussion we recommend that for future work the use of models should be accompanied by a discussion of the effect that model and data uncertainty have on the model results. We also suggest that future field work incorporate repeat occupations of sample sites on time scales of 1–4 weeks in order to evaluate steady state versus non-steady state estimates of ²³⁴Th export, especially during high flux events (> ca. 800 dpm m^− 2 d^− 1). Finally, knowledge of the physical oceanography of the study area is essential, particularly in ocean margins and in areas of established upwelling (e.g., Equatorial Pacific). These suggestions will greatly enhance the application of ²³⁴Th as a tracer of particle dynamics and flux in more complicated regimes.