Biological Control of Chromium Redox and Stable Isotope Composition in the Surface Ocean.

While chromium stable isotopes (δ53Cr) have received significant attention for their utility as a tracer of oxygen availability in the distant geological past, a mechanistic understanding of modern oceanic controls on Cr and δ53Cr is still lacking. Here we present total dissolved δ53Cr, concentrations of Cr (III) and total dissolved Cr, and net community productivity (NCP) from the North Pacific. Chromium concentrations show surface depletions in waters with elevated NCP, but not in lower productivity waters. Observed Cr deficits correspond well with calculated Cr export derived from NCP and Cr:C ratios of natural phytoplankton and marine particulates. Chromium (III) concentrations are stable over the diel cycle yet correlate with NCP, with maxima found in highly productive surface waters but not in lower productivity waters, indicating biological control on Cr (III). The relationship between Cr (III) and δ53Cr suggests that δ53Cr distributions may be controlled by the removal of isotopically light Cr (III) at an isotopic enrichment factor (∆53Cr) of -1.08‰ ± 0.25 relative to total dissolved δ53Cr, in agreement with the global δ53Cr-Cr fractionation factor (-0.82‰ ± 0.05). No perturbation to δ53Cr, Cr, or Cr (III) is observed in oxygen-depleted waters (~10 µmol/kg), suggesting no strong control by O2 availability, in agreement with other recent studies. Therefore, we propose that biological productivity is the primary control on Cr and δ53Cr in the modern ocean. Consequently, δ53Cr records in marine sediments may not faithfully record oxygen availability in the Late Quaternary. Instead, our data demonstrate that δ53Cr records may be a useful tracer for biological productivity.

Young organic matter as a source of carbon dioxide outgassing from Amazonian rivers.

Rivers are generally supersaturated with respect to carbon dioxide, resulting in large gas evasion fluxes that can be a significant component of regional net carbon budgets. Amazonian rivers were recently shown to outgas more than ten times the amount of carbon exported to the ocean in the form of total organic carbon or dissolved inorganic carbon. High carbon dioxide concentrations in rivers originate largely from in situ respiration of organic carbon, but little agreement exists about the sources or turnover times of this carbon. Here we present results of an extensive survey of the carbon isotope composition (13C and 14C) of dissolved inorganic carbon and three size-fractions of organic carbon across the Amazonian river system. We find that respiration of contemporary organic matter (less than five years old) originating on land and near rivers is the dominant source of excess carbon dioxide that drives outgassing in medium to large rivers, although we find that bulk organic carbon fractions transported by these rivers range from tens to thousands of years in age. We therefore suggest that a small, rapidly cycling pool of organic carbon is responsible for the large carbon fluxes from land to water to atmosphere in the humid tropics.

Synoptic Mesoscale to Basin Scale Variability in Biological Productivity and Chlorophyll in the Kuroshio Extension Region.

The Kuroshio current separates from the Japanese coast to become the eastward flowing Kuroshio Extension (KE) characterized by a strong latitudinal density front, high levels of mesoscale (eddy) energy, and high chlorophyll a (Chl). While satellite measurements of Chl show evidence of the impact of mesoscale eddies on the standing stock of phytoplankton, there have been very limited synoptic, spatially resolved in situ estimates of productivity in this region. Here, we present underway measurements of oxygen/argon supersaturation (ΔO2/Ar), a tracer of net biological productivity, for the KE made in spring, summer, and early autumn. We find large seasonal differences in the relationships between ΔO2/Ar, Chl, and sea level anomaly (SLA), a proxy for local thermocline depth deviations driven by mesoscale eddies derived from satellite observations. We show that the KE is a pronounced hotspot of high ΔO2/Ar in spring, but corresponding surface Chl values are low and have no correlation with ΔO2/Ar. In summer, there is a hotspot of productivity associated with the Oyashio front, where ΔO2/Ar and Chl are strongly positively correlated. In autumn, ΔO2/Ar and Chl are consistently low throughout the region and also positively correlated. By combining our analysis of the in situ ΔO2/Ar data with complementary Argo, BGC-Argo, repeat hydrography, and SLA observations, we infer the combination of physical and biological controls that drive the observed distributions of ΔO2/Ar and Chl. We find that the KE and Oyashio currents both act to supply nutrients laterally, fueling regions of high productivity in spring and summer, respectively.

The oligotrophic ocean is autotrophic.

In vitro observations of net community production (NCP) imply that the oligotrophic subtropical gyres of the open ocean are net heterotrophic; in situ observations, in contrast, consistently imply that they are net autotrophic. At least one approach must be returning an incorrect answer. We find that (a) no bias in in situ oxygen-based production estimates would give false-positive (net autotrophy) rates, (b) observed (13)C enrichment of surface water dissolved inorganic carbon (DIC) can be explained only by positive NCP (net autotrophy), (c) lateral and vertical inputs of organic carbon are insufficient to sustain net heterotrophy, and (d) atmospheric input of organic material is too small to support in vitro rates of net heterotrophy and would yield δ(13)C depletion of surface DIC, quite the opposite of what is observed in the subtropical gyres. We conclude that the in vitro observations, implying net heterotrophy, must contain a bias that is due to an underestimate of photosynthetic rate and/or an overestimate of respiration rate.

Mesoscale eddies drive increased silica export in the subtropical Pacific Ocean.

Mesoscale eddies may play a critical role in ocean biogeochemistry by increasing nutrient supply, primary production, and efficiency of the biological pump, that is, the ratio of carbon export to primary production in otherwise nutrient-deficient waters. We examined a diatom bloom within a cold-core cyclonic eddy off Hawaii. Eddy primary production, community biomass, and size composition were markedly enhanced but had little effect on the carbon export ratio. Instead, the system functioned as a selective silica pump. Strong trophic coupling and inefficient organic export may be general characteristics of community perturbation responses in the warm waters of the Pacific Ocean.

Isotopic analysis of atmospheric formaldehyde by gas chromatography isotope ratio mass spectrometry.

Little is known about the isotopic composition of formaldehyde in the atmosphere, a chemical intermediate in hydrocarbon oxidation. Here, we present a promising new method to analyze the carbon (delta 13C) and hydrogen (delta D) isotopic composition of atmospheric formaldehyde. The direct isotopic analytical technique described uses continuous-flow gas chromatography-isotope ratio mass spectrometry, which provides flexibility for either isotopic analysis without correction for derivative functional groups. Current levels of precision of measurement are +/-1.1 and +/-50 per thousand (1 sigma) for delta 13C and delta D analyses, respectively. Concentration of formaldehyde in ambient air is also determined, coincident with isotopic measurement, to a precision of +/-15%. The method has the required sensitivity for analyses of formaldehyde in urban air on relatively small volume grab samples of whole air (10-70L STP), potentially providing high temporal resolution. This is particularly advantageous for studying formaldehyde given its short lifetime and large variability in the atmosphere.