James S. Kuwabara

Authigenic molybdenum formation in marine sediments: a link to pore water sulfide in the Santa Barbara Basin

Pore water and sediment Mo concentrations were measured in a suite of multicores collected at four sites along the northeastern flank of the Santa Barbara Basin to examine the connection between authigenic Mo formation and pore water sulfide concentration. Only at the deepest site (580 m), where pore water sulfide concentrations rise to .0.1 mM right below the sediment water interface, was there active authigenic Mo formation. At shallower sites (550, 430, and 340 m), where pore water sulfide concentrations were consistently ,0.05 mM, Mo precipitation was not occurring at the time of sampling. A sulfide concentration of ;0.1 mM appears to be a threshold for the onset of Mo-Fe-S co-precipitation. A second threshold sulfide concentration of;100 mM is required for Mo precipitation without Fe, possibly as Mo-S or as particle-bound Mo. Mass budgets for Mo were constructed by combining pore water and sediment results for Mo with analyses of sediment trap material from Santa Barbara Basin as well as sediment accumulation rates derived from 210 Pb. The calculations show that most of the authigenic Mo in the sediment at the deepest site is supplied by diffusion from overlying bottom waters. There is, however, a non-lithogenic particulate Mo associated with sinking particles that contributes #15% to the total authigenic Mo accumulation. Analysis of sediment trap samples and supernant brine solutions indicates the presence of non-lithogenic particulate Mo, a large fraction of which is easily remobilized and, perhaps, associated with Mn-oxides. Our observations show that even with the very high flux of organic carbon reaching the sediment of Santa Barbara Basin, active formation of sedimentary authigenic Mo requires a bottom water oxygen concentration below 3 mM. However, small but measurable rates of authigenic Mo accumulation were observed at sites where bottom water oxygen ranged between 5 and 23 mM, indicating that the formation of authigenic Mo occurred in the recent past, but not at the time of sampling. Copyright

Trace Metal Associations in the Water Column of South San Francisco Bay, California

Spatial distributions of copper (Cu), zinc (Zn) and cadmium (Cd) were followed along a longitudinal gradient of dissolved organic carbon (DOC) in South San Francisco Bay (herein referred to as the South Bay). Dissolved Cu, Zn and Cd concentrations ranged from 24 to 66 nM, from 20 to 107 nM and from 1·2 to 4·7 nM, respectively, in samples collected on five dates beginning with the spring phytoplankton bloom and continuing through summer,1985. Dissolved Cu and Zn concentrations varied indirectly with salinity and directly with DOC concentration which ranged from 2·1 to 4·1 mg l−1. Available thermodynamic data strongly support the hypothesis that Cu speciation may be dominated by association with dissolved organic matter. Analogous control of Zn speciation by organic complexation was, however, not indicated in our computations. Computed free ion activity estimates for Cu, Zn and Cd were of the order of 10−10, 10−8 and 10−10 M, respectively. The availability of these metals may be among the factors regulating the growth of certain phytoplankton species within this region of the estuary. In contrast to dissolved Cu, dissolved Cd was directly related to the concentration of suspended particulate matter, suggesting a source of dissolved Cd coincident with elevated particle concentrations in the South Bay (e.g. runoff and solute desorption). Consistent with work in other estuaries, partitioning of all three trace metals onto suspended particulates was negatively correlated with salinity and positively correlated with increases in particulate organic carbon associated with the phytoplankton bloom. These results for the South Bay indicate that sorption processes influence dissolved concentrations of these trace metals, the degree of this influence varies among metals, and processes controlling metal distribution in this estuary appear to be more element-specific than spatially- or temporally-specific.

Dissolved sulfide distributions in the water column and sediment pore waters of the Santa Barbara Basin

Abstract Dissolved sulfide concentrations in the water column and in sediment pore waters were measured by square-wave voltammetry (nanomolar detection limit) during three cruises to the Santa Barbara Basin in February 1995, November–December 1995, and April 1997. In the water column, sulfide concentrations measured outside the basin averaged 3 ± 1 nM (n = 28) in the 0 to 600 m depth range. Inside the basin, dissolved sulfides increased to reach values of up to 15 nM at depths >400 m. A suite of box cores and multicores collected at four sites along the northeastern flank of the basin showed considerable range in surficial ( 400 μM at 10 cm. Decreases in water-column nitrate below the sill depth indicate nitrate consumption (−55 to −137 μmole m−2 h−1) similar to nearby Santa Monica Basin. Peaks in pore-water iron concentrations were generally observed between 2 and 5 cm depth with shallowest peaks at the 590 m site. These observations, including observations of the benthic microfauna, suggest that the extent to which the sulfide flux, sustained by elevated pore-water concentrations, reaches the water column may be modulated by the abundance of sulfide-oxidizing bacteria in addition to iron redox and precipitation reactions.

Phosphorus-zinc interactive effects on growth by Selenastrum capricornutum (Chlorophyta).

Culturing experiments in chemically defined growth media were conducted to observe possible Zn and P interactions on Selenastrum capricornutum Printz growth indexes. Elevated Zn concentrations (7.5 x 10/sup -8/ and 1.5 x 10/sup -7/ M (Zn/sup 2 +/)) were highly detrimental to algal growth, affecting lag, exponential, and stationary growth phases. P behaved as a yield-limiting nutrient with maximum cell densities increasing linearly with total P. This yield limitation was intensified at elevated Zn concentrations. Although calculated cellular phosphorus concentrations increased markedly with Zn ion activity, elevated Zn concentrations had no apparent effect on rates of phosphorus uptake estimated for Selenastrum during exponential growth. Results indicated that P-Zn interactions were significant in describing Selenastrum cell yield results and are consistent with previous Zn studies on chlorophytes. These P-Zn interactions and the observed inhibitory growth effects of submicromolar Zn concentrations suggest that in nature an apparent P yield-limiting condition may result from elevated Zn concentrations.

Development of a mercury speciation, fate, and biotic uptake (BIOTRANSPEC) model: Application to Lahontan Reservoir (Nevada, USA)

A mathematically linked mercury transport, speciation, kinetic, and simple biotic uptake (BIOTRANSPEC) model has been developed. An extension of the metal transport and speciation (TRANSPEC) model, BIOTRANSPEC estimates the fate and biotic uptake of inorganic (Hg(II)), elemental (Hg(0)) and organic (MeHg) forms of mercury and their species in the dissolved, colloidal (e.g., dissolved organic matter [DOM]), and particulate phases of surface aquatic systems. A pseudo-steady state version of the model was used to describe mercury dynamics in Lahontan Reservoir (near Carson City, NV, USA), where internal loading of the historically deposited mercury is remobilized, thereby maintaining elevated water concentrations. The Carson River is the main source of total mercury (THg), of which more than 90% is tightly bound in a gold-silver-mercury amalgam, to the system through loadings in the spring, with negligible input from the atmospheric deposition. The speciation results suggest that aqueous species are dominated by Hg-DOM, Hg(OH)(2), and HgClOH. Sediment-to-water diffusion of MeHg and Hg-DOM accounts for approximately 10% of total loadings to the water column. The water column acts as a net sink for MeHg by reducing its levels through two competitive processes: Uptake by fish, and net MeHg demethylation. Although reservoir sediments produce significant amounts of MeHg (4 g/d), its transport from sediment to water is limited (1.6 g/d), possibly because of its adsorption on metal oxides of iron and manganese at the sediment-water interface. Fish accumulate approximately 45% of the total MeHg mass in the water column, and 9% of total MeHg uptake by fish leaves the system because of fishing. Results from this new model reiterate the previous conclusion that more than 90% of THg input is retained in sediment, which perpetuates elevated water concentrations.

CULTURING MICROSCOPIC STAGES OF MACROCYSTIS PYRIFERA (PHAEOPHYTA) IN AQUIL, A CHEMICALLY DEFINED MEDIUM

Requirements of Macrocystis pyrifera (L.) C. A. Agardh (giant kelp) for nine nutrient elements (N, P, Mn, Fe, Co, Cu, Zn, Mo, I) were established by batch culturing settled spores, through the gametophytic phase, to production of embryonic sporophytes in Aquil, a chemically defined, artificial seawater medium. The ultimately successful medium resulted from ten sequential culturing series, applying an optimization technique to improve each succeeding formulation.

Dissolved sulfides in the oxic water column of San Francisco Bay, California

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

Micronutrients and Kelp Cultures: Evidence for Cobalt and Manganese Deficiency in Southern California Deep Seawater

It has been suggested that naturally occurring copper and zinc concentrations in deep seawater are toxic to marine organisms when the free ion forms are overabundant. The effects of micronutrients on the growth of gametophytes of the ecologically and commercially significant giant kelp (Macrocystis pyrifera) were studied in defined media. The results indicate that toxic copper and zinc ion concentrations as well as cobalt and manganese deficiencies may be among the factors controlling the growth of marine organisms in nature.

A study of metal ion adsorption at low suspended-solid concentrations

A procedure for conducting adsorption studies at low suspended solid concentrations in natural waters (<50 mg l−1) is described. Methodological complications previously associated with such experiments have been overcome. Adsorption of zinc ion onto synthetic colloidal titania (TiO2) was studied as a function of pH, supporting electrolyte (NaCl) concentration (0·1-0·002 m) and particle concentration (2–50 mg l−1). The lack of success of the Davis Leckie site bonding model in describing Zn(II) adsorption emphasizes the need for further studies of adsorption at low suspended-solid concentrations.

Benthic nutrient sources to hypereutrophic Upper Klamath Lake, Oregon, USA

Three collecting trips were coordinated in April, May, and August 2006 to sample the water column and benthos of hypereutrophic Upper Klamath Lake (OR, USA) through the annual cyanophyte bloom of Aphanizomenon flos-aquae. A pore-water profiler was designed and fabricated to obtain the first high-resolution (centimeter-scale) estimates of the vertical concentration gradients of macro- and micronutrients for diffusive-flux determinations. A consistently positive benthic flux for soluble reactive phosphorus (SRP) was observed with solute release from the sediment, ranging between 0.4 and 6.1 mg/m(2)/d. The mass flux over an approximate 200-km(2) lake area was comparable in magnitude to riverine inputs. An additional concern related to fish toxicity was identified when dissolved ammonium also displayed consistently positive benthic fluxes of 4 to 134 mg/m(2)/d, again comparable to riverine inputs. Although phosphorus was a logical initial choice by water quality managers for the limiting nutrient when nitrogen-fixing cyanophytes dominate, initial trace-element results from the lake and major inflowing tributaries suggested that the role of iron limitation on primary productivity should be investigated. Dissolved iron became depleted in the lake water column during the course of the algal bloom, while dissolved ammonium and SRP increased. Elevated macroinvertebrate densities, at least of the order of 10(4) individuals/m(2), suggested that the diffusive-flux estimates may be significantly enhanced by bioturbation. In addition, heat-flux modeling indicated that groundwater advection of nutrients could also significantly contribute to internal nutrient loading. Accurate environmental assessments of lentic systems and reasonable expectations for point-source management require quantitative consideration of internal solute sources.