Atmospheric nitrate concentrations and isotope composition for samples collected in the marine boundary layer in 2006 and 2007

The comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the d15N of nitrate mostly deriving from anthropogenically emitted NOx is found to be significantly different (from 0 to 6 per mil) from nitrate sampled in locations influenced by natural NOx sources (-4 ± 2) per mil. The effects on d15N(NO3-) of different NOx sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (D17O = d17O - 0.52 × d18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NOx sinks. Different D17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low d15N values (down to -40 per mil) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NOx from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores.

Chlorophyll a concentration in plankton, biomass of different taxonomic phytoplankton groups, dominating algae species, and some parameters of coastal surface waters of the Black Sea

Based on data obtained at three stations in coastal waters of the Black Sea off Sevastopol in 2000 and 2001, we present seasonal dynamics of the carbon to chlorophyll a ratio in nano- and microphy-toplankton. This parameter varied approximately tenfold throughout the year. Its maximum values (442-500) were obtained in summer (July), when Pyrrophyta dominated in phytoplankton. Minimum values (36-56) were observed in winter (December),when diatomaceous species predominated. We derive a regression relating the carbon to chlorophyll a ratio to proportion of Pyrrophyta in total phytoplankton biomass, doing so separately for warm and cold seasons. Regression equations demonstrate coupled action of irradiance, temperature, and nutrient availability on the carbon to chlorophyll a ratio. For Pyrrophyta phytoplankton assemblage R**2 = 0.95, and for diatomaceous one R**2 = 0.87.

Experiment: Elevated CO2 levels affect the activity of nitrate reductase and carbonic anhydrase in the calcifying rhodophyte Corallina officinalis

The concentration of CO2 in global surface ocean waters is increasing due to rising atmospheric CO2 emissions, resulting in lower pH and a lower saturation state of carbonate ions. Such changes in seawater chemistry are expected to impact calcification in calcifying marine organisms. However, other physiological processes related to calcification might also be affected, including enzyme activity. In a mesocosm experiment, macroalgal communities were exposed to three CO2 concentrations (380, 665, and 1486 µatm) to determine how the activity of two enzymes related to inorganic carbon uptake and nutrient assimilation in Corallina officinalis, an abundant calcifying rhodophyte, will be affected by elevated CO2 concentrations. The activity of external carbonic anhydrase, an important enzyme functioning in macroalgal carbon-concentrating mechanisms, was inversely related to CO2 concentration after long-term exposure (12 weeks). Nitrate reductase, the enzyme responsible for reduction of nitrate to nitrite, was stimulated by CO2 and was highest in algae grown at 665 µatm CO2. Nitrate and phosphate uptake rates were inversely related to CO2, while ammonium uptake was unaffected, and the percentage of inorganic carbon in the algal skeleton decreased with increasing CO2. The results indicate that the processes of inorganic carbon and nutrient uptake and assimilation are affected by elevated CO2 due to changes in enzyme activity, which change the energy balance and physiological status of C. officinalis, therefore affecting its competitive interactions with other macroalgae. The ecological implications of the physiological changes in C. officinalis in response to elevated CO2 are discussed.

(Table 1) Concentration of iron, DIP and silicic acid in water samples taken during Nathaniel B. Palmer cruises NBP06-01 and NBP06-08 (CORSACS I+II), Ross Sea

The Ross Sea polynya is among the most productive regions in the Southern Ocean and may constitute a significant oceanic CO2 sink. Based on results from several field studies, this region has been considered seasonally iron limited, whereby a "winter reserve" of dissolved iron (dFe) is progressively depleted during the growing season to low concentrations (~0.1 nM) that limit phytoplankton growth in the austral summer (December-February). Here we report new iron data for the Ross Sea polynya during austral summer 2005-2006 (27 December-22 January) and the following austral spring 2006 (16 November-3 December). The summer 2005-2006 data show generally low dFe concentrations in polynya surface waters (0.10 ± 0.05 nM in upper 40 m, n = 175), consistent with previous observations. Surprisingly, our spring 2006 data reveal similar low surface dFe concentrations in the polynya (0.06 ± 0.04 nM in upper 40 m, n = 69), in association with relatively high rates of primary production (~170-260 mmol C/m**2/d). These results indicate that the winter reserve dFe may be consumed relatively early in the growing season, such that polynya surface waters can become "iron limited" as early as November; i.e., the seasonal depletion of dFe is not necessarily gradual. Satellite observations reveal significant biomass accumulation in the polynya during summer 2006-2007, implying significant sources of "new" dFe to surface waters during this period. Possible sources of this new dFe include episodic vertical exchange, lateral advection, aerosol input, and reductive dissolution of particulate iron.