Determination of the Electrochemical Properties of a Soluble Aqueous FeS Species Present in Sulfidic Solutions

Field and laboratory data are presented that show a soluble FeS species(FeS_aq) exists in sulfidic seawater solutions, and is observedwhen the IAP exceeds the K_sp of amorphous FeS. TheFeS_aq yields a discrete signal (double peak) using square-wavevoltammetry and two one-electron waves in sampled DC polarographyexperiments at the Hg electrode. The aqueous FeS species reacts irreversiblyat the electrode as a single FeS subunit and not as a polymeric entity. Thepeak potential of FeS_aq occurs at -1.1 V whereas the peakpotential of Fe occurs at-1.45 V; the positive shift for Fe²⁺ reduction inFeS_aq indicates a change in geometry for Fe²⁺from octahedral to tetrahedral. The kinetics of electron transfer at theelectrode are determined to be similar for both Fe²⁺ andFeS_aq. Molecular orbital energy diagrams, further indicatethat Fe(II) does change from octahedral to tetrahedral geometry in solution.First, Fe(II) exists as octahedralFe in solution whichundergoes a substitution reaction of bisulfide for water. The resultingcomplex, Fe(H₂O)₅(HS)⁺, thentransforms to a tetrahedral complex on further addition of sulfide. Thisgeometry change is consistent with the formation of amorphous FeS thatconverts to mackinawite which has tetrahedral Fe(II). The process is entropydriven because of the water loss that occurs. The overall sequence can berepresented as: Soluble FeS species are important asreactants in the formation of iron-sulfide minerals including pyrite.     

Short-term variability of suspended sediment and phytoplankton in Tampa Bay,Florida: Observations from a coastal oceanographic tower and ocean color satellites

We examined short-term phytoplankton and sediment dynamics in Tampa Bay with data collected between 8 December 2004 and 17 January 2005 from optical, oceanographic, and meteorological sensors mounted on a coastal oceanographic tower and from satellite remote sensing. Baseline phytoplankton (chlorophyll-a, Chl) and sediment concentrations (particle backscattering coefficient at 532 nm, bbp(532)) were of the order of 3.7 mg m⁻³ and 0.07 m⁻¹, respectively, during the study period. Both showed large fluctuations dominated by semidiurnal and diurnal frequencies associated with tidal forcing. Three strong wind events (hourly averaged wind speed >8.0 m s⁻¹) generated critical bottom shear stress of >0.2 Pa and suspended bottom sediments that were clearly observed in concurrent MODIS satellite imagery. In addition, strong tidal current or swells could also suspend sediments in the lower Bay. Sediments remained suspended in the water column for 2–3 days after the wind events. Moderate Chl increases were observed after sediment resuspension with a lag time of ˜1–2 days, probably due to release of bottom nutrients and optimal light conditions associated with sediment resuspension and settling. Two large increases in Chl with one Chl > 12.0 mg m⁻³ over ˜2 days, were observed at neap tides. For the study site and period, because of the high temporal variability in phytoplankton and sediment concentrations, a monthly snapshot can be different by −50% to 200% from the monthly “mean” chlorophyll and sediment conditions. The combination of high-frequency observations from automated sensors and synoptic satellite imagery, when available, is an excellent complement to limited field surveys to study and monitor water quality parameters in estuarine environments.     

Molecular iodine reduction by natural and model organic substances in seawater

The reactivity of 2 µM molecular iodine in seawater toward various organic compounds containing aromatic, -keto, amino, olefinic and sugar functional groups was investigated. More detailed studies have been made of the reduction kinetics with salicylic acid, -ketoglutaric acid and the polypeptide oxidized glutathione, particularly to establish whether variation over the pH range 4–9 would provide a similar reduction reactivity or fingerprint to that of molecular iodine added to natural seawater. The data indicates that compounds with only one functional group react with first order kinetics whereas compounds with multiple functional groups show more complex behaviour. Kinetic and thermodynamic modelling indicates that HOI is the main iodine species reacting with organic matter at seawater pH of 8.2. Based on the pH fingerprints, peptides and compounds containing carbonyl or -keto groups are the key reductants of molecular iodine added to seawater. These compounds form C-I and N-I bonds which can allow for a rich organic iodine chemistry in seawater. The model compound results are discussed in relation to oceanic processes.     

Determination of inorganic sulphur speciation with polarographic techniques: Some preliminary results for recent hypersaline anoxic sediments

Polarographic techniques have been used to determine reduced inorganic sulphur speciation in recent anoxic marine sediments from two hypersaline basins, the Tyro and the Bannock Basins, in the Eastern Mediterranean. The following phases were determined: acid volatile sulphur (AVS), pyritic sulphur and zerovalent sulphur. The determination of AVS and pyrite was based respectively on the acidification and Cr(II) reduction of these sulphur components to H₂S. H₂S was collected in base and the sulphide concentration was measured by polarography. Standard Na₂S and pyrite gave recoveries of 99.6% ± 3.9% and 97% ± 12% respectively. Total zerovalent sulphur in a sediment sample was measured by the reaction of sulphite with thiosulphate. Thiosulphate was measured directly by polarography.

Pyrite is the main phase of inorganic reduced sulphur in the sediments from the Tyro and the Bannock Basins, and it has about the same average level (125 υmoles per gramme dry weight) in the cores recovered from the two areas. However, the distribution of pyrite in the top 100 cm of the two cores differs significantly. In the Bannock Basin a sharp increase is observed with depth, whereas in the Tyro Basin there is a small decrease with depth.

The total amount of reduced inorganic sulphur is less than the total amount of sulphur in the sediments. This indicates that there must be additional sulphur-bearing phases. One of these phases may be gypsum, and indeed, gypsum crystals have been observed in the Bannock Basin.

In neither basin is there a significant correlation between reduced sulphur and organic carbon. The pyrite that occurs in these basins may have been formed syngenetically at the interface of the anoxic brine and oxic seawater. Diagenetic pyrite may have been formed within the sediments of the basins. AVS and total zerovalent sulphur are still observed at depth. We therefore suggest that this may be due to the incomplete transformation of AVS and zerovalent sulphur into pyrite.     

Peripheral communities of the Eastern Lau Spreading Center and Valu Fa Ridge: community composition,temporal change and comparison to near‐vent communities

Western Pacific hydrothermal vents will soon be subjected to deep‐sea mining and peripheral sites are considered the most practical targets. The limited information on community dynamics and temporal change in these communities makes it difficult to anticipate the impact of mining activities and recovery trajectories. We studied community composition of peripheral communities along a cline in hydrothermal chemistry on the Eastern Lau Spreading Center and Valu Fa Ridge (ELSC‐VFR) and also studied patterns of temporal change. Peripheral communities located in the northern vent fields of the ELSC‐VFR are significantly different from those in the southern vent fields. Higher abundances of zoanthids and anemones were found in northern peripheral sites and the symbiont‐containing mussel Bathymodiolus brevior, brisingid seastars and polynoids were only present in the northern peripheral sites. By contrast, certain faunal groups were seen only in the southern peripheral sites, such as lollipop sponges, pycnogonids and ophiuroids. Taxonomic richness of the peripheral communities was similar to that of active vent communities, due to the presence of non‐vent endemic species that balanced the absence of species found in areas of active venting. The communities present at waning active sites resemble those of peripheral sites, indicating that peripheral species can colonize previously active vent sites in addition to settling in the periphery of areas of venting. Growth and mortality were observed in a number of the normally slow‐growing cladorhizid stick sponges, indicating that these animals may exhibit life history strategies in the vicinity of vents that differ from those previously recorded. A novel facultative association between polynoids and anemones is proposed based on their correlated distributions.     

Campo del Cielo modeling and comparison with observations: II. Funnels and craters

The Campo del Cielo impact structure exhibits several penetration funnels and impact craters. Here, we model the formation of these funnels with pre-impact conditions consistent with the results of meteoroid entry models. We study vertical impacts to find the dependence of funnel geometry (depth, diameter) on impact velocity and target porosity. At velocities above 1 km s⁻¹, we observe strong deformation of the projectile and transformation of funnels into regular impact craters. We also use 3-D impact models to study oblique impacts and find that in the case of impact angles <25° to the horizon, the projectile bounces off the target. Instead of a funnel, an elongated groove forms, while the fragmented projectile escapes and moves farther downrange. At steeper impact angles, funnels form with the projectile at its tip. Early interpretations of the Campo del Cielo impact angle at 9–10° were based on (i) an oversimplified atmospheric model allowing “correct” strewn field elongation and (ii) the results of excavation in which the sloping boundary between breccia-like materials and infilling loess was interpreted as a true crater floor and its slope was equated to the impact angle. As our models show, the projectile trajectory within the target is not a straight line, and the angle to horizon changes from a steep one at the impact point to zero and then to a negative value (the projectile is moving upward). We also model two impact craters (Hoyo de la Cañada and Laguna Negra) created by high-velocity fragments to demonstrate the projectile remnants ricochet in the downrange direction.     

Metal–organic complexation in the marine environment

We discuss the voltammetric methods that are used to assess metal–organic complexation in seawater. These consist of titration methods using anodic stripping voltammetry (ASV) and cathodic stripping voltammetry competitive ligand experiments (CSV-CLE). These approaches and a kinetic approach using CSV-CLE give similar information on the amount of excess ligand to metal in a sample and the conditional metal ligand stability constant for the excess ligand bound to the metal. CSV-CLE data using different ligands to measure Fe(III) organic complexes are similar. All these methods give conditional stability constants for which the side reaction coefficient for the metal can be corrected but not that for the ligand. Another approach, pseudovoltammetry, provides information on the actual metal–ligand complex(es) in a sample by doing ASV experiments where the deposition potential is varied more negatively in order to destroy the metal–ligand complex. This latter approach gives concentration information on each actual ligand bound to the metal as well as the thermodynamic stability constant of each complex in solution when compared to known metal–ligand complexes. In this case the side reaction coefficients for the metal and ligand are corrected. Thus, this method may not give identical information to the titration methods because the excess ligand in the sample may not be identical to some of the actual ligands binding the metal in the sample.     

ATR-FTIR spectroscopic studies of boric acid adsorption on hydrous ferric oxide

Boron is an important micronutrient for plants, but high B levels in soils are often responsible for toxicity effects in plants. It is therefore important to understand reactions that may affect B availability in soils. In this study, Attenuated Total Reflectance Fourier transform Infrared (ATR-FTIR) spectroscopy was employed to investigate mechanisms of boric acid (B(OH)₃) and borate (B(OH)₄⁻) adsorption on hydrous ferric oxide (HFO). On the HFO surface, boric acid adsorbs via both physical adsorption (outer-sphere) and ligand exchange (inner-sphere) reactions. Both trigonal (boric acid) and tetrahedral (borate) boron are complexed on the HFO surface, and a mechanism where trigonal boric acid in solution reacts to form either trigonal or tetrahedral surface complexes is proposed based upon the spectroscopic results. The presence of outer-sphere boric acid complexes can be explained based on the Lewis acidity of the B metal center, and this complex has important implications for boron transport and availability. Outer-sphere boric acid is more likely to leach downward in soils in response to water flow. Outer-sphere boron would also be expected to be more available for plant uptake than more strongly bound boron complexes, and may more readily return to the soil solution when solution concentrations decrease.     

Biomass mapping using forest type and structure derived from Landsat TM imagery

A method for mapping forest biomass was developed and tested on a study area in western Newfoundland, Canada. The method, BIOmass from Cluster Labeling Using Structure and Type (BioCLUST), involves: (i) hyperclustering a Landsat TM image, (ii) automatically labeling the clusters with information about forest type and structure, and (iii) applying stand-level equations that estimate biomass as a function of height and crown closure within forest species-type classes. BioCLUST was validated with biomass values measured at geo-referenced field plots and mapped across the study area using an existing forest management photo-inventory. Root mean square error (RMSE) values ranged from 43 to 79 tonnes/ha, and were lowest for intermediate height classes when validated with field plots. Overall bias was negative at 10 tonnes/ha compared with a negative bias of 3 tonnes/ha estimated for the photo-inventory. Validation of the biomass map gave RMSE values of 37–47 tonnes/ha and overall landscape biomass estimates within 0.4% of biomass mapped by the photo-inventory. BioCLUST offers an alternative to other biomass mapping methods when scene-specific plot data are limited and a photo-inventory is available for a representative portion of a Landsat scene.