Kenneth H. Coale

What controls dissolved iron concentrations in the world ocean

Dissolved ( value in the data set at a depth near 750 m, where variability is at a maximum. The minimum concentrations are found at stations in the remote central Pacific and the maximum values occur at stations adjacent to the continental margin. The major source of iron in the deep sea is generally aeolian deposition. Integrated (surface to 500 m) concentrations of iron at each station are only weakly correlated with the aeolian iron deposition flux, however. This contrasts with other elements such as lead that also have strong atmospheric sources. These observations lead us to conclude that the nutrient-like profile is maintained by a mechanism that reduces the scavenging rate of dissolved iron at concentrations less than 0.6 nmol kg- ’ This mechanism may be complexation by strong iron binding ligands, which have been found in both the Atlantic and Pacific at concentrations near 0.6 nM. This apparent solubility would act to diminish inter-ocean fractionation. It would allow a nutrient-like profile to develop before scavenging began to remove iron. In order to test the concept, we developed a numerical model to make quantitative predictions of dissolved iron concentrations from place to place. The dissolved iron source in the ocean interior is remineralization from sinking particulate organic matter. Scavenging removes dissolved iron only at concentrations greater than the apparent solubility. The only geographically variable parameter in the model is the export flux of carbon from the surface layer, which carries iron with it. The model generated dissolved iron profiles, based on measured or estimated values of the carbon export flux, are in remarkable agreement with the observed profiles at all stations from the North Atlantic through the Southern Ocean to the North Pacific. 0 1997 Elsevier Science B.V.

Synthesis of iron fertilization experiments: From the Iron Age in the Age of Enlightenment

Comparison of eight iron experiments shows that maximum Chl a, the maximum DIC removal, and the overall DIC/Fe efficiency all scale inversely with depth of the wind mixed layer (WML) defining the light environment. Moreover, lateral patch dilution, sea surface irradiance, temperature, and grazing play additional roles. The Southern Ocean experiments were most influenced by very deep WMLs. In contrast, light conditions were most favorable during SEEDS and SERIES as well as during IronEx-2. The two extreme experiments, EisenEx and SEEDS, can be linked via EisenEx bottle incubations with shallower simulated WML depth. Large diatoms always benefit the most from Fe addition, where a remarkably small group of thriving diatom species is dominated by universal response of Pseudo-nitzschia spp. Significant response of these moderate (10–30 μm), medium (30–60 μm), and large (>60 μm) diatoms is consistent with growth physiology determined for single species in natural seawater. The minimum level of “dissolved” Fe (filtrate < 0.2 μm) maintained during an experiment determines the dominant diatom size class. However, this is further complicated by continuous transfer of original truly dissolved reduced Fe(II) into the colloidal pool, which may constitute some 75% of the “dissolved” pool. Depth integration of carbon inventory changes partly compensates the adverse effects of a deep WML due to its greater integration depths, decreasing the differences in responses between the eight experiments. About half of depth-integrated overall primary productivity is reflected in a decrease of DIC. The overall C/Fe efficiency of DIC uptake is DIC/Fe ∼ 5600 for all eight experiments. The increase of particulate organic carbon is about a quarter of the primary production, suggesting food web losses for the other three quarters. Replenishment of DIC by air/sea exchange tends to be a minor few percent of primary CO2 fixation but will continue well after observations have stopped. Export of carbon into deeper waters is difficult to assess and is until now firmly proven and quite modest in only two experiments.

Geochemistry of barium in marine sediments : Implications for its use as a paleoproxy

Abstract Variations in the accumulation rate of barium in marine sediments are thought to be indicative of variations in marine biological productivity through time. However, the use of Ba as a proxy for paleoproductivity is partly dependent upon its being preserved in the sediment record in a predictable or consistent fashion. Arguments in favor of high Ba preservation are partly based on the assumption that sediment porewaters are generally at saturation with respect to pure barite. The idea is that because nondetrital sedimentary Ba predominantly exists as barite, porewater saturation would promote burial. We present sediment porewater, sediment solid phase, and benthic incubation chamber data suggesting that solid-phase Ba preservation may be compromised in some geochemical settings. We propose that under suboxic diagenetic conditions, characterized by low bottom water oxygen and high organic carbon respiration rates, Ba preservation may be reduced. Independent of the mechanism, if this assertion is true, then it becomes important to know when the Ba record is unreliable. We present evidence demonstrating that the sedimentary accumulation of authigenic U may serve as a proxy for when the Ba record is unreliable. We then provide an example from the Southern Ocean during the last glacial period where high authigenic U concentrations coincide with high Pa:Th ratios and high accumulation rates of biogenic opal, but we find low accumulation rates of sedimentary Ba. Thus, for the study sites presented here during the last glacial, we conclude that Ba is an unreliable productivity proxy.

Developing standards for dissolved iron in seawater

In nearly a dozen open- ocean fertilization experiments conducted by more than 100 researchers from nearly 20 countries, adding iron at the sea surface has led to distinct increases in photosynthesis rates and biomass. These experiments confirmed the hypothesis proposed by the late John Martin [Martin, 1990] that dissolved iron concentration is a key variable that controls phytoplankton processes in ocean surface waters. However, the measurement of dissolved iron concentration in seawater remains a difficult task [Bruland and Rue, 2001] with significant interlaboratory differences apparent at times. The availability of a seawater reference solution with well- known dissolved iron (Fe) concentrations similar to open- ocean values, which could be used for the calibration of equipment or other tasks, would greatly alleviate these problems [National Research Council (NRC), 2002]. The Sampling and Analysis of Fe (SAFe) cruise was staged from Honolulu, Hawaii, to San Diego, Calif., between 15 October and 8 November 2004 to collect data and samples that were later used to provide this reference material. Here we provide a brief report on the cruise results, which have produced a tenfold improvement in the variability of iron measurements, and announce the availability of the SAFe dissolved Fe in seawater standards.

ANALYSIS OF SEAWATER FOR DISSOLVED CADMIUM, COPPER AND LEAD: AN INTERCOMPARISON OF VOLTAMMETRIC AND ATOMIC ABSORPTION METHODS

An intercomparison study of voltammetric and atomic absorption spectrometric methods for determining cadmium, lead and copper in seawater samples was conducted. The voltammetric approach utilizes differential pulse anodic stripping voltammetry using a rotating, glassy carbon, mercury film electrode under conditions developed to minimize contamination sources and to enhance sensitivity for seawater matrices. The atomic absorption approach involves a concentration step using either an organic solvent extraction of metal dithiocarbamate chelates or a Chelex-100 column with detection by graphite furnace atomic absorption spectrometry. Similar and consistent results were obtained using both methods for the three trace metals studied on a wide range of natural seawater samples. Both methods are comparable in sensitivity for cadmium and copper, however the voltammetric method is better suited for the analysis of lead in seawater because of its enhanced sensitivity and low blank. An advantage of the voltammetric approach is its amenability towards real-time shipboard analysis.

Iron photochemistry in seawater from the equatorial Pacific

Abstract The photochemistry of iron in surface waters, and its implications to iron bioavailability, was examined on two cruises to the equatorial Pacific. Decktop incubations were performed with equatorial seawater to which iron was added in various chemical forms. Results showed clear diurnal patterns in measurable iron levels, with the highest levels occurring midday. These results are consistent with a model of iron cycling involving the photo-reductive dissolution of colloidal iron and its subsequent oxidation and biological uptake of dissolved iron(III). Model calculations were based on independently determined rate constants. We suggest that photochemical reactions may have a significant impact on iron availability to phytoplankton in the open ocean.

Phosphorus regeneration in continental margin sediments

Benthic incubation chambers have been deployed in a variety of geochemical environments along the California Continental Margin. These include both high and low oxygen environments and sites where the rate of organic matter oxidation on the seafloor (Cox) ranges from < 1 mmol m−2 day−1 to more than 7 mmol m−2 day−1 through a depth range of 100–3500 m. This range in the rate of organic matter oxidation along with variations in the concentration of bottom water oxygen allow us to elucidate the diagenetic conditions under which P regeneration may be decoupled from organic matter cycling. Under conditions where bottom water oxygen concentration is low (<50 μM), and the rate of organic matter oxidation is also low (< 1 mmol m−2 day−1), P regeneration may be less than that expected from the decay of organic debris and, in some cases, there is a flux of phosphate into the sediments. At stations where bottom water oxygen is low, and the degradation rate of organic material is greater than 1 mmol m−2 day−1, phosphate may be released at a rate exceeding the production expected from the oxidation of organic matter. At stations having high bottom water oxygen concentrations, rates of organic matter decomposition < ∼7 mmol m−2 day−1, and where benthic irrigation is not significant, P regeneration is consistent with that expected from the decomposition of organic debris. In addition, our data indicate that high benthic iron fluxes are observed in regions exhibiting a decoupling between organic matter and phosphate, whereas low to zero iron fluxes are observed in regions where P regeneration is either consistent with or less than that expected from the decomposition of organic material. These results support previous work suggesting a coupling between iron cycling and phosphate cycling in suboxic environments. Data presented here show that this coupling may result in either preferential phosphate burial or release relative to organic material in suboxic environments.

Trace metal concentrations in the Ross Sea and their relationship with nutrients and phytoplankton growth

Abstract Dissolved and particulate trace metal concentrations (dissolved Fe, Zn, Cd, Co, Cu and Ni; particulate Fe, Mn and Al) were measured along two transects in the Ross Sea during austral summer of 1990. Total Fe concentrations in southern Ross Sea and inshore waters were elevated >3.5 times that of northern waters. Dissolved Zn, Cd and Co concentrations were lower by factors of 4.5, 3.5 and 1.6 in southern surface waters relative to northern waters. Dissolved Cu and Ni concentrations were similar in both areas. Elevated Fe concentrations coincided with areas of increased productivity, phytoplankton biomass and nutrient drawdown, indicating that Fe is an important factor controlling the location of phytoplankton blooms in the Ross Sea. Particulate concentrations of Fe, Mn and Al indicate two possible sources of iron to the Ross Sea, resuspension of continental shelf sediments and iron incorporated in annual sea ice and released with meltwaters.

Spatial and temporal variability in copper complexation in the North Pacific

Abstract The complexation of trace metals by organic ligands has long been proposed to play a significant role in determining trace metal speciation in seawater. However, analytical methodologies with sufficient specificity and sensitivity only recently have been developed to enable us to address questions of trace metal/organic complexation. In this study copper titrations were conducted at sea using differential pulse anodic stripping voltammetry on North Pacific samples to determine the extent of copper complexation with organic ligands. This study includes data from a transect from 33°N, 139°W to 55°N, 148°W and seasonal occupations of the VERTEX T-4 station (33°N, 139°W). The data indicate the presence of at least two copper binding ligands: L 1 , the stronger ligand, or ligand class, averages 2 nM with log K ′ l cond(Cu′) = 11.6; L 2 , the weaker ligand class varies between 5 and 10 nM witgh log K ′ 2 cond(Cu′) = 8.6. The presence of these ligands strongly buffers the activity of copper(II) in surface waters at all stations. Seasonal variations in the distribution of strong copper complexing ligands follow seasonal variations in the depth of the mixed layer at T-4 and indicate a ligand source in the lower mixed layer. Ligand concentrations do not covary with the rates of primary productivity in a latitudinal transect from the central North Pacific to the subarctic. Ligand concentrations at all stations vary only by a factor of two and hold surface water copper(II) ion activities relatively constant (about 10 −14 M), suggestive of a regulated ligand production mechanism. These results comprise a unique data set for copper complexation in the Pacific and may have significantly implications for the distribution of plankton between oligotrophic and subarctic systems.

Age, growth and radiometric age validation of a deep-sea, habitat-forming gorgonian (Primnoa resedaeformis) from the Gulf of Alaska

Sustainable fisheries require (1) viable stock populations with appropriate harvest limits and (2) appropriate habitat for fish to survive, forage, seek refuge, grow and reproduce. Some deep-water habitats, such as those formed by deep-water stands of coral, may be vulnerable to fishing disturbance. The rate at which habitat can be restored is a critical aspect of fishery management. The purpose of this study was to characterize growth rates for a habitat-forming deep-sea coral. Two nearly complete colonies of red tree coral (Primnoa resedaeformis) collected from waters off southeast Alaska were used for an analysis of age and growth characteristics. CAT scans revealed that colonies consisted of multiple settlement events, where older basal structures provided for settlement of new colonies. The decay of 210Pb over the length of the colony was used to validate age estimates from growth ring counts. Age estimates were over 100 yr for sections near the heavily calcified base. Based on validated growth ring counts, growth of red tree coral ranged from 1.60 to 2.32 cm per year in height and was approximately 0.36 mm per year in diameter. These growth rates suggest that the fishery habitat created by red tree coral is extremely vulnerable to bottom fishing activities and may take over 100 years to recover.