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In July 2002, a combination of underway mapping and discrete profiles revealed significant along-shore variability in the concentrations of manganese and iron in the vicinity of Monterey Bay, California. Both metals had lower concentrations in surface waters south of Monterey Bay, where the shelf is about 2.5 km wide, than north of Monterey Bay, where the shelf is about 10 km wide. During non-upwelling conditions over the northern broad shelf, dissolvable iron concentrations measured underway in surface waters reached 3.5 nmol L−1 and dissolved manganese reached 25 nmol L−1. In contrast, during non-upwelling conditions over the southern narrow shelf, dissolvable iron concentrations in surface waters were less than 1 nmol L−1 and dissolved manganese concentrations were less than 5 nmol L−1. A pair of vertical profiles at 1000 m water depth collected during an upwelling event showed dissolved manganese concentrations of 10 decreasing to 2 nmol L−1, and dissolvable iron concentrations of 12–20 nmol L−1 in the upper 100 m in the north, compared to 3.5–2 nmol L−1 Mn and ∼0.6 nmol L−1 Fe in the upper 100 m in the south, suggesting the effect of shelf width influences the chemistry of waters beyond the shelf. These observations are consistent with current understanding of the mechanism of iron supply to coastal upwelling systems: Iron from shelf sediments, predominantly associated with particles greater than 20 μm, is brought to the surface during upwelling conditions. We hypothesize that manganese oxides are brought to the surface with upwelling and are then reduced to dissolved manganese, perhaps by photoreduction, following a lag after upwelling. Greater phytoplankton biomass, primary productivity, and nutrient drawdown were observed over the broad shelf, consistent with the greater supply of iron. Incubation experiments conducted 20 km offshore in both regions, during a period of wind relaxation, confirm the potential of these sites to become limited by iron. There was no additional growth response when copper, manganese or cobalt was added in addition to iron. The growth response of surface water incubated with bottom sediment (4 nmol L−1 dissolvable Fe) was slightly greater than in control incubations, but less than in the presence of 4 nmol L−1 dissolved iron. This may indicate that dissolvable iron is not as bioavailable as dissolved iron, although the influence of additional inhibitory elements in the sediment cannot be ruled out.

The availability of iron is known to exert a controlling influence on biological productivity in surface waters over large areas of the ocean and may have been an important factor in the variation of the concentration of atmospheric carbon dioxide over glacial cycles. The effect of iron in the Southern Ocean is particularly important because of its large area and abundant nitrate, yet iron-enhanced growth of phytoplankton may be differentially expressed between waters with high silicic acid in the south and low silicic acid in the north, where diatom growth may be limited by both silicic acid and iron. Two mesoscale experiments, designed to investigate the effects of iron enrichment in regions with high and low concentrations of silicic acid, were performed in the Southern Ocean. These experiments demonstrate iron's pivotal role in controlling carbon uptake and regulating atmospheric partial pressure of carbon dioxide.

We report measurements of dissolvable and particulate iron, particulate Al, nutrients and phytoplankton biomass in surface waters during the termination of one upwelling event and the initiation of a second event in August 2000. These events occurred in the area of the Ano Nuevo upwelling center off the coast of central California. The first event was observed after ∼8 days of continuous upwelling favorable winds, while the second event was observed through the onset of upwelling favorable winds to wind reversals ∼3 days later. Coincident with the upwelling signatures of low temperature and high salinity were significantly elevated concentrations of nitrate and silicate with average concentrations greater than 15 and 20 μM, respectively, during both upwelling events. Dissolvable Fe concentrations (TD-Fe) were significantly higher in the second event, 6.5 versus 1.2 nM Fe found in the first event. Nitrate was reduced by ∼5 μM day −1 within this second upwelled plume as compared to a drawdown of ∼2 μM day −1 within the first plume. Silicate was reduced in a ratio of 1.2 mol Si:mol NO 3 in the high Fe waters of the second plume as compared to a ratio of 2.2 in the lower Fe waters of the first plume. The observed differences in nutrient utilization are consistent with some degree of iron limitation. The area of increased dissolvable Fe in the second upwelling event was coincident with elevated particulate Fe concentrations, indicating the particulate pool as a possible source of the observed increase in TD-Fe. The elevated particulate Fe in surface waters was a result of resuspended sediments in the bottom boundary layer (BBL) of the shallow shelf being transported to the surface during upwelling. Particulate (and dissolvable) iron concentrations were significantly reduced as upwelling continued. This was most probably due to a decoupling of the BBL from upwelled source waters as the upwelling front moved offshore and/or reduced turbulence in the BBL as upwelling continued. The observed reduction in both particulate and dissolvable Fe, as upwelling continued to deliver macronutrients to surface waters, may result in varying levels of Fe limitation.

Iron has been measured for 16 months with ∼21 day resolution at three stations in the upwelling ecosystem of central California, providing the first detailed assessment of the annual iron cycle in the coastal zone. A large pulse of iron occurs during the first spring upwelling event of the year. Iron concentrations then decay up to 100-fold over several months, although upwelling continues. Excess surface nitrate and low iron are the result during the summer and fall at the two stations furthest offshore (20 and 45 km), while nitrate is depleted and iron high nearshore (5 km). Phytoplankton biomass, primary production and community structure appear to be controlled by iron concentrations in offshore waters during this period.

The idea that iron might limit phytoplankton growth in large regions of the ocean has been tested by enriching an area of 64 km2 in the open equatorial Pacific Ocean with iron. This resulted in a doubling of plant biomass, a threefold increase in chlorophyll and a fourfold increase in plant production. Similar increases were found in a chlorophyll-rich plume down-stream of the Galapagos Islands, which was naturally enriched in iron. These findings indicate that iron limitation can control rates of phytoplankton productivity and biomass in the ocean.

In situ measurements of dissolved manganese and total dissolved iron were conducted in hydrothermal plumes over the Juan de Fuca Ridge using a submersible chemical analyzer (Scanner). The Scanner was deployed as part of a CTD/transmissometer/rosette instrument package on both tow-yos and vertical casts during the VENTS Leg I cruise in 1989. Dissolved manganese and total dissolved iron concentrations, along with temperature and light attenuation anomalies, were determined over the ridge crest every 5 s. Discrete samples for laboratory analyses of dissolved iron II, total dissolved iron II+III and manganese were also collected. Metal to heat ratios (Me:Q) measured in situ were extremely variable in one steady state plume, while an event plume had constant Me:Q. Uniform values of Mn:Q in the event plume demonstrate that Mn behaves conservatively in the near-field plume. Variability in the Mn: Q ratios in a steady state plume indicated the presence of at least two hydrothermal sources with distinct Me:Q values. A simple mixing model shows that the contribution of Mn from high Me:Q sources, with a composition characteristic of black smoker vents, varies between 1% and 99% within the core of the steady state plume with an average value of 55%. On average, over 50% of the excess heat within the plume originates from low Me:Q ratio sources, with a composition characteristic of low-temperature, diffuse flow vent fluids. Less than 4% of the volume of hydrothermal fluids in the plume originates from black smokers. The Fe II concentrations were used to provide an estimate of plume age on a transect across the ridge axis. Plume ages were about 2.5 days on axis and >12 days off axis. These plume ages were modeled to provide estimates of plume transport and horizontal diffusion and show excellent agreement with ages determined using 222Rn.

[1] Seven years of observations of surface water iron concentrations in the Monterey Bay region of central California reveal a consistent annual cycle dominated by the injection of high concentrations of particulate iron each spring. A companion study of the water column near the upwelling center at the north end of the bay clearly indicates a sedimentary source for the iron. Local river discharge, during winter storm events, results in the deposition of a fine-grained sediment “fluff” layer along the shelf. The initial rapid shoaling of isotherms at the onset of upwelling in spring brings water from the fluff layer to the surface. Concentrations of iron in both surface and source waters are then quickly diminished although upwelling intensifies, bringing the highest concentration of nitrate to the surface ∼3 months later. The concentration of a number of constituents measured in bottom water samples collected during the companion study strongly suggests that the rapid decrease in surface water iron concentrations is due to the depletion of the fluff layer following initial isotherm shoaling. The decoupling of iron and nitrate supply sets up the potential for iron limitation. However, on the basis of average Fe/NO3 ratios, we conclude that the region is not often iron limited. Iron limitation was apparent only one summer at the offshore station. Summer chlorophyll concentrations are highly correlated to dissolvable (unfiltered) iron concentrations, evidence in support of the role of particulate iron in meeting the ecosystem's iron requirements.

[1] The flux of dissolved iron from sediments to the water column was measured with flux chambers along the California coast over a five-year period. High fluxes were observed from sediments on the continental shelf. The measured fluxes were an average of 75 times larger than flux values derived from pore-water iron gradients. The iron flux was significantly correlated with the oxidation of organic matter, which allows an extrapolation to the global shelf. The input from shelf sediments is at least as significant as the global input of dissolved iron from aerosols, which has been presumed to be the dominant external iron source. Evidence of this input is seen 100's of kilometers offshore where it can enable the high productivity of broad coastal regions seen in satellite images.

[1] Here we report measurements of iron and aluminum in surface and subsurface waters during late March and late May of 2001 on transects between central California and Hawaii. A large cloud of Asian dust was detected during April 2001, and there was a clear signal in surface water iron due to aerosol deposition on the May transect. Iron and aluminum concentrations increased synchronously by 0.5 and 2 nM along the southern portion of the transect, which includes the Hawaii Ocean Time series (HOT) station, from background values in March (0.1 to 0.2 nM Fe). These changes occurred in a ratio that is close to the crustal abundance ratio of the metals, which indicates a soil aerosol source. A vertical profile of dissolved iron was also measured at the HOT station in late April and this profile also shows a large increase near the surface. Direct observations of aerosol iron concentration at Mauna Loa Observatory on Hawaii indicate that aerosol concentrations were significantly lower than climatological values during this period. Soil aerosol concentrations along the transect were estimated using the real-time Navy Aerosol Analysis and Prediction System (NAAPS). The NAAPS results show a large meridional gradient with maximum concentrations in the boundary layer north of 30°N. However, the deposition of iron and aluminum to surface waters was highest south of 25°N, near Hawaii. There were only weak signals in the ecosystem response to the aerosol deposition.

The flux of manganese from continental margin sediments to the ocean was measured with a free-vehicle, benthic flux chamber in a transect across the continental shelf and upper slope of the California margin. The highest fluxes were observed on the shallow continental shelf. Manganese flux decreased linearly with bottom water oxygen concentration, and the lowest fluxes occurred in the oxygen minimum zone (at a depth of 600 to 1000 meters). Although the flux of manganese from continental shelf sediments can account for the elevated concentrations observed in shallow, coastal waters, the flux from sediments that intersect the oxygen minimum cannot produce the subsurface concentration maximum of dissolved manganese that is observed in the Pacific Ocean.