Calibration of a chalcogenide glass membrane ion-selective electrode for the determination of free Fe in seawater: I. Measurements in UV photooxidised seawater

Calibration of a chalcogenide glass membrane, Fe(III)ISE [Fe_2.5(Ge₂₈Sb₁₂Se₆₀)_97.5], in buffered saline media has been undertaken in order to assess the suitability of this ISE for seawater analyses. The electrode slopes in saline citrate and salicylate buffers were 26.3 and 28.2 mV/decade, respectively, for Fe³⁺ concentrations ranging from 10⁻¹⁰ M to less than 10⁻²⁵ M Fe³⁺. The calibration lines in the citrate and salicylate buffers were essentially collinear with the response in unbuffered chloride-free standards containing >10⁻⁵ M Fe³⁺, demonstrating that the response of the FeISE is unaffected by chloride ions. A mechanism involving a combination of charge transfer and ion-exchange of Fe(III), at the electrode diffusion layer, can be used to explain the ≈30 mV/decade slope of the FeISE. The response of the FeISE in UV photooxidised seawater containing 8 nM total Fe was measured as the pH was changed from 8.27 to 3.51. The slope of the response was 24.2 mV/decade [Fe³⁺] calculated as a function of pH using Fe(III) hydrolysis constants for seawater. Moreover, the response was essentially collinear with that in citrate buffers and in unbuffered solutions containing >10⁻⁵ M Fe³⁺ and the slope for the combined data was 26.2 mV/decade. This study was restricted to organic-free seawater because the certainty in Fe(III)–ligand stability constants is insufficient to warrant the selection of an ideal calibration buffer system, and there is evidence that powerful chelating ligands (e.g., EDTA along with humic and fulvic acids) may alter the response of the Fe(III)ISE. The Fe dissolution rate of the FeISE in UV photooxidised seawater was found to be 1.6×10⁻² nmol Fe/min, as measured by cathodic stripping voltammetry (CSV). This would contaminate a 100-ml sample by 0.8–1.6 nM Fe over a typical measurement period of 5–10 min obtained using a stability criterion of 0.5 mV/min. Various methods are proposed for reducing the level of contamination in open ocean samples that contain sub-nanomolar concentrations of iron. The FeISE has the potential to detect free Fe³⁺ at concentrations typically found in natural seawater.     

Holocene reef growth in Torres Strait

The platform and fringing reefs of Torres Strait are morphologically similar to reefs of the northern Great Barrier Reef to the south, except that several are elongated in the direction of the strong tidal currents between the Coral Sea and the Gulf of Carpentaria. Surface and subsurface investigations and radiocarbon dating on Yam, Warraber and Hammond Islands reveal that the initiation and mode of Holocene reef growth reflect antecedent topography and sea-level history. On the granitic Yam Island, fringing reefs have established in some places over a Pleistocene limestone at about 6 m depth around 7000 years BP. Emergent Holocene microatolls of Porites sp. indicate that the reefs have prograded seawards while sea level has fallen gradually from at least 0.8 m above present about 5800 years BP. On the Warraber Island reef platform drilling near the centre indicated a Pleistocene limestone foundation at a depth of about 6 m over which reefs established around 6700 years BP. Reef growth lagged behind that on Yam Island. Microatolls on the mature reef flat indicate that the reef reached sea level around 5300 years BP when the sea was around 0.8–1.0 m above present. On the reef flat on the western side of Hammond Island bedrock was encountered at 7–8 m depth, overlain by terrigenous mud. A progradational reef sequence of only 1–2 m thickness has built seaward over these muds, as sea level has fallen over the past 5800 years. Reef-flat progradation on these reefs is interpreted to have occurred by a series of stepwise buildouts marked by lines of microatolls parallel to the reef crest, marking individual coalescing coral heads. Detrital infill has occurred between these. This pattern of reef progradation is consistent with the radiocarbon dating results from these reefs, and with seismic investigations on the Torres Reefs.     

The requirements for stable metallothionein clusters examined using synthetic lobster domains.

Metallothioneins (MTs) are small, cysteine-rich proteins which detoxify xenobiotic metals such as cadmium (Cd) and mercury (Hg). In crustaceans and mammals they consist of two independent domains which are folded around metal-thiolate clusters. MT clusters of different origins, exhibiting distinct, highly conserved cysteine positions on their sequences, show differences in metal-cysteine coordination and reactivity. Lobster-MT, containing two Cd3 beta domains, is an important model for structure-function relationships among the clusters. The influence of (1) the position of the cysteine residues and (2) steric and electrostatic effects of neighboring amino acids on the folding and stability of MT cluster were investigated. Thus, the native lobster beta C and beta N domains (each having nine cysteines and binding three M2+ ions) and a modified domain Cd3 beta C-->N, in which the cysteines of the C-terminal domain were relocated to match the positions of those in the N-terminal domain, were chemically prepared and characterized. The synthetic native domains (Cd3 beta C and Cd3 beta N) were found to exhibit spectroscopic properties, metal-binding affinities and kinetic reactivity similar to the holo-protein. However, the modified Cd3 beta C-->N domain was unusually reactive and in the presence of Chelex, metal chelation resin, aggregated to a Cd5(beta C-->N)2 dimer, which exhibited unusual structure as observed by its 113Cd-nuclear magnetic resonance. These differences in structure and reactivity demonstrated that the requirements for formation of a stable Cd3S9 beta-cluster are more stringent than simply the sequential positions of the cysteines along the peptide chain and must include interactions involving neighboring, noncysteine amino acids.     

Stable carbon isotope distribution of particulate organic matter in the ocean: a model study

The stable carbon isotopic composition of particulate organic matter in the ocean, δ¹³C_POC, shows characteristic spatial variations with high values in low latitudes and low values in high latitudes. The lowest δ¹³C_POC values (−32‰ to −35‰) have been reported in the Southern Ocean, whereas in arctic and subarctic regions δ¹³C_POC values do not drop below −27‰. This interhemispheric asymmetry is still unexplained. Global gradients in δ¹³C_POC are much greater than in δ¹³C_DIC, suggesting that variations in isotopic fractionation during organic matter production are primarily responsible for the observed range in δ¹³C_POC. Understanding the factors that control isotope variability is a prerequisite when applying δ¹³C_POC to the study of marine carbon biogeochemistry. The present model study attempts to reproduce the δ¹³C_POC distribution pattern in the ocean. The three-dimensional (3D) Hamburg Model of the Oceanic Carbon Cycle version 3.1 (HAMOCC3.1) was combined with two different parametrizations of the biological fractionation of stable carbon isotopes. In the first parametrization, it is assumed that the isotopic fractionation between CO₂ in seawater and the organic material produced by algae, _P, is a function of the ambient CO₂ concentration. The two parameters of this function are derived from observations and are not based on an assumption of any specific mechanism. Thus, this parametrization is purely empirical. The second parametrization is based on fractionation models for microalgae. It is supported by several laboratory experiments. Here the fractionation, _P, depends on the CO₂ concentration in seawater and on the (instantaneous) growth rates, μ_i, of the phytoplankton. In the Atlantic Ocean, where most field data are available, both parametrizations reproduce the latitudinal variability of the mean δ¹³C_POC distribution. The interhemispheric asymmetry of δ¹³C_POC can mostly be attributed to the interhemispheric asymmetry of CO₂ concentration in the water. However, the strong seasonal variations of δ¹³C_POC as reported by several authors, can only be explained by a growth rate-dependent fractionation, which reflects variations in the cellular carbon demand.