Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay

A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.     

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.     

Iodine chemistry in deep anoxic basins and overlying waters of the Mediterranean Sea

Iodate (IO₃⁻) is the predominant dissolved species of iodine in the oxygenated waters of the Mediterranean Sea. Iodide (I⁻) is present in significant quantities (up to 65 nM) in oxygenated waters in the photic zone and near the interface above the anoxic and saline Bannock Basin. Lesser quantities of I⁻ (< 10 nM) are found throughout the rest of the oxic water column. An additional unidentified dissolved iodine species is present immediately above the anoxic interface.Total dissolved iodine (ΣI) increases dramatically across the seawater/brine interface. Part of this increase is undoubtedly the result of the dissolution of iodine-rich evaporites during formation of the brine bodies at the Tyro and Bannock Basins. The vertical distribution of ΣI and other dissolved chemical species (particularly PO₄³⁻) in the Bannock Basin brine, however, suggests an additional, present-day, diagenetic source of dissolved iodine to the brine. Based on the increase in the concentration of the most soluble major ions across the seawater/brine interface, 5–7 μM of the 11.5-μM increase in ΣI concentration must be attributed to diagenesis.     

A Numerical Simulation of Residual Circulation in Tampa Bay. Part II: Lagrangian Residence Time

Lagrangian retention and flushing are examined by advecting neutrally buoyant point particles within a circulation field generated by a numerical ocean model of Tampa Bay. Large temporal variations in Lagrangian residence time are found under realistic changes in boundary conditions. Two 90-day time periods are examined. The first (P1) is characterized by low freshwater inflow and weak baroclinic circulation. The second (P2) has high freshwater inflow and strong baroclinic circulation. At the beginning of both time periods, 686,400 particles are released uniformly throughout the bay. Issues relating to particle distribution and flushing are examined at three different spatial scales: (1) at the scale of the entire bay, (2) the four major regions within the bay, and (3) at the scale of individual model grid cells. Two simple theoretical models for the particle number over time, N(t), are fit to the particle counts from the ocean model. The theoretical models are shown to represent N(t) reasonably well when considering the entire bay, allowing for straightforward calculation of baywide residence times: 156 days for P1 and 36 days for P2. However, the accuracy of these simple models decreases with decreasing spatial scale. This is likely due to the fact that particles may exit, reenter, or redistribute from one region to another in any sequence. The smaller the domain under consideration, the more this exchange process dominates. Therefore, definitions of residence time need to be modified for “non-local” situations. After choosing a reasonable definition, and removal of the tidal and synoptic signals, the residence times at each grid cell in P1 is found to vary spatially from a few days to 90 days, the limit of the calculation, with an average residence time of 53 days. For P2, the overall spatial pattern is more homogeneous, and the residence times have an average value of 26 days.     

Changes in the circulation of Tampa Bay due to Hurricane Frances as recorded by ADCP measurements and reproduced with a numerical Ocean model

Hurricane Frances is shown to greatly alter the hydrodynamics within Tampa Bay, Florida, and the exchange of water with the Gulf of Mexico in both observational data and a realistic numerical circulation model of the Tampa Bay estuary. Hurricane Frances hit Tampa Bay on September 5, 2004 with surface winds peaking twice near 22 m s⁻¹. There were three stages to the hydrodynamic effect of Frances on Tampa Bay. The first stage included the approach of Frances up to the first wind peak. The winds were to the south and southeast. During this stage sea level was maintained below mean sea level (MSL) and the residual current (demeaned, detided) was weak. The second stage began as the winds turned to the east and northeast, as the eye passed near the bay, and ended as the second wind peak appeared. During this stage the residual currents were strongly positive (into the bay), raising sea level to 1.2 m above MSL at St. Petersburg. The measured residual circulation peaked at over +0.7 m s⁻¹ near the surface. The model shows this velocity peak yielded a maximum volume flux into the bay of +44,227 m³ s⁻¹, displacing a total volume of 1.5 billion m³ in just a few hours, about 42% of the bay volume. In the third stage a strong negative flow developed as the wind and sea level relaxed to near normal levels. The ADCP measured a peak outflow of −0.8 m s⁻¹ during this time. Model results indicate a maximum flux of −37,575 m³ s⁻¹, and that it took about 50 h to drain the extra volume driven into the bay by Hurricane Frances.     

ENSO impacts on salinity in Tampa Bay, Florida

Estuarine salinity distributions reflect a dynamic balance between the processes that control estuarine circulation. At seasonal and longer time scales, freshwater inputs into estuaries represent the primary control on salinity distribution and estuarine circulation. El Niño-Southern Oscillation (ENSO) conditions influence seasonal rainfall and stream discharge patterns in the Tampa Bay, Florida region. The resulting variability in freshwater input to Tampa Bay influences its seasonal salinity distribution. During El Niño events, ENSO sea surface temperature anomalies (SSTAs) are significantly and inversely correlated with salinity in the bay during winter and spring. These patterns reflect the elevated rainfall over the drainage basin and the resulting elevated stream discharge and runoff, which depress salinity levels. Spatially, the correlations are strongest at the head of the bay, especially in bay sections with long residence times. During La Niña conditions, significant inverse correlations between ENSO SSTAs and salinity occur during spring. Dry conditions and depressed stream discharge characterize La Niña winters and springs, and the higher salinity levels during La Niña springs reflect the lower freshwater input levels.     

Iron and Sulfur Chemistry in a Stratified Lake: Evidence for Iron-Rich Sulfide Complexes

A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment. Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as [Fe(H₂O)₆]²⁺ or free H₂S as H₂S/HS^- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H₂S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe₂SH³⁺ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom waters are similar to the pK_sp of mackinawite. Soluble iron-sulfide species are stable in the absence of O₂ (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes can react with O₂ to oxidize sulfide and can also dissociate releasing volatile H₂S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/gr_{dry wt}) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich sulfide complexes.     

Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

Sublittoral seaweed communities on natural and artificial substrata in a high-latitude coral community in South Africa

Coral mortality may result in macroalgal proliferation or a phase shift into an alga-dominated state. Subtidal, high-latitude western Indian Ocean coral communities at Sodwana Bay on the KwaZulu-Natal coast, South Africa, have experienced some mortality because of warm-water anomalies, storms and other causes, but the response of the macroalgae is unknown. We investigated the abundance and diversity of benthic algae on different hard natural substrata (dead digitate, brain and plate corals and beach rock) on Two-Mile Reef, Sodwana Bay. We also compared algal communities colonising ceramic, marble and pretreated ceramic tiles placed on the reef for six months. We identified 95 algae (14 Chlorophyta, 11 Phaeophyceae, 69 Rhodophyta and one cyanobacterium). Assemblages on natural and artificial substrata were dominated by the brown alga Lobophora variegata (Lamouroux) Womersley ex Oliveira and non-geniculate corallines (Rhodophyta, Corallinaceae). Cluster and ordination analyses revealed that the algae showed no affinity for particular substrata, whether natural or artificial. Algal cover was occasionally higher on rougher tiles and crustose corallines were significantly more abundant on marble than ceramic tiles. Two-Mile Reef had 23.1% dead and 48.4% live scleractinian coral cover, where dead corals were colonised indiscriminately by many small algal species, but there was no evidence of algal proliferation. The results provide a baseline for monitoring this high-latitude reef system.