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Increasing atmospheric carbon dioxide is driving a long-term decrease in ocean pH which is superimposed on daily to seasonal variability. These changes impact ecosystem processes, and they serve as a record of ecosystem metabolism. However, the temporal variability in pH is observed at only a few locations in the ocean because a ship is required to support pH observations of sufficient precision and accuracy. This paper describes a pressure tolerant Ion Sensitive Field Effect Transistor pH sensor that is based on the Honeywell Durafet ISFET die. When combined with a AgCl pseudoreference sensor that is immersed directly in seawater, the system is capable of operating for years at a time on platforms that cycle from depths of several km to the surface. The paper also describes the calibration scheme developed to allow calibrated pH measurements to be derived from the activity of HCl reported by the sensor system over the range of ocean pressure and temperature. Deployments on vertical profiling platforms enable self-calibration in deep waters where pH values are stable. Measurements with the sensor indicate that it is capable of reporting pH with an accuracy of 0.01 or better on the total proton scale and a precision over multiyear periods of 0.005. This system enables a global ocean observing system for ocean pH.

Eukaryotic algae within the picoplankton size class (≤2 μm in diameter) are important marine primary producers, but their spatial and ecological distributions are not well characterized. Here, we studied three picoeukaryotic prasinophyte genera and their cyanobacterial counterparts, Prochlorococcus and Synechococcus , during two cruises along a North Pacific transect characterized by different ecological regimes. Picoeukaryotes and Synechococcus reached maximum abundances of 1.44 × 10 5 and 3.37 × 10 5 cells · ml −1 , respectively, in mesotrophic waters, while Prochlorococcus reached 1.95 × 10 5 cells · ml −1 in the oligotrophic ocean. Of the picoeukaryotes, Bathycoccus was present at all stations in both cruises, reaching 21,368 ± 327 18S rRNA gene copies · ml −1 . Micromonas and Ostreococcus clade OI were detected only in mesotrophic and coastal waters and Ostreococcus clade OII only in the oligotrophic ocean. To resolve proposed Bathycoccus ecotypes, we established genetic distances for 1,104 marker genes using targeted metagenomes and the Bathycoccus prasinos genome. The analysis was anchored in comparative genome analysis of three Ostreococcus species for which physiological and environmental data are available to facilitate data interpretation. We established that two Bathycoccus ecotypes exist, named here BI (represented by coastal isolate Bathycoccus prasinos ) and BII. These share 82% ± 6% nucleotide identity across homologs, while the Ostreococcus spp. share 75% ± 8%. We developed and applied an analysis of ecomarkers to metatranscriptomes sequenced here and published -omics data from the same region. The results indicated that the Bathycoccus ecotypes cooccur more often than Ostreococcus clades OI and OII do. Exploratory analyses of relative transcript abundances suggest that Bathycoccus NRT2.1 and AMT2.2 are high-affinity NO 3 − and low-affinity NH 4 + transporters, respectively, with close homologs in multiple picoprasinophytes. Additionally, in the open ocean, where dissolved iron concentrations were low (0.08 nM), there appeared to be a shift to the use of nickel superoxide dismutases (SODs) from Mn/Fe/Cu SODs closer inshore. Our study documents the distribution of picophytoplankton along a North Pacific ecological gradient and offers new concepts and techniques for investigating their biogeography.

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.

Manganese oxidation rates were determined at low (∼ 20 nM) concentrations in seawater by measuring dissolved manganese (Mn(II)) using flow injection analysis with chemiluminescence detection. Mn(II) was measured in samples that had been filtered (0.2 μm) and kept in the dark under controlled temperature and pH conditions for time periods up to 6 months. Eight 9 L carboys with mean pH values ranging from 8 to 8.7 were held at 25°C, another carboy (pH = 9.32) was kept at 5°C. Oxidation followed the Morgan (1967) homogeneous rate equation (d[Mn(II)]/dt = k1 [O2][OH−]2[Mn(II)]). The mean rate constant k1 = 1.7 ± 0.7 × 1012 M−3 d−1 (95% CI), determined using hydroxide ion activities determined with pH measurements on the NBS scale, was in agreement with work by Morgan (1967; k1 = 4 × 1012 M−3 d−1) and Davies and Morgan (1989; k1 = 1.1 × 1012 M−3 d−1) in dilute solutions. The rate constant at 5°C was 1.3 ± 0.3 × 1012 M−3 d−1. If free hydroxide concentrations (based on the free proton pH scale) are used, then the rate constant at 25°C was k 1 ∗ = 0.34 ± 0.14 × 10 12 M−3d−1. Autocatalytic increases in Mn(II) oxidation rates, as predicted by a heterogeneous reaction mechanism (Morgan, 1967) (d[Mn(II)]/dt= k2′[Mn(II)][MnO2]) were not observed, indicating that the homogeneous reaction dominates Mn(II) oxidation at low nM concentrations in seawater. Bacteria were enumerated by 4′,6-diamidino-2-phenylindole (DAPI) staining during the experiments. No significant correlation between bacterial concentrations and Mn(II) oxidation rates was found.

A sensitive technique for the shipboard determination of zinc in seawater has been developed. The technique couples flow injection analysis with fluorometric detection (FIA-FL). A cation exchange column was used to separate zinc from interering alkali and alkaline earth ions and to concentrate Zn from seawarer. The organic indicator ligan, p-tosyl-8-aminoquinoline, was used to form a complex with zinc, the fluorescence of which was determined with a flow-through fluorometer. The deterction limit (defined as three times the standard deviation of the blank, n=4) was 0.1 nM for a 4.4-mL sample

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.

The light is emitted by the reaction of brillant sulfoflavin with hydrogen peroxide and Fe(II) in a neutral medium. A cation-exchange column is used to preconcentrate the iron from seawater. The detection limit was 0.45 nmol/L when 4.4 mL of sample was passed through the column

[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.