Vertical profiles of nitrous oxide and dissolved oxygen in marine sediments

The whole core squeezing method was used to simultaneously obtain profiles of nitrous oxide (N₂O), nitrogenous nutrients, and dissolved oxygen in sediments of Koaziro Bay, Japan (coastal water), the East China Sea (marginal sea), and the central Pacific Ocean (open ocean). In the spring of Koaziro Bay, subsurface peaks of interstitial N₂O (0.5–3.5 cm depth) were observed, at which concentrations were higher than in the overlying water. This was also true for nitrate (NO₃⁻) and nitrite (NO₂⁻) profiles, suggesting that the transport of oxic overlying water to the depth through faunal burrows induced in situ N₂O production depending on nitrification. In the summer of Koaziro Bay, sediment concentrations of N₂O, NO₃⁻ and NO₂⁻ were lower than in the overlying water. In most East China Sea sediments, both N₂O and NO₃⁻ decreased sharply in the top 0.5–2 cm oxic layer (oxygen: 15–130 μM), which may have indicated N₂O and NO₃⁻ consumption by denitrification at anoxic microsites. N₂O peaks at subsurface depth (0.5–6.5 cm) implied in situ production of N₂O and/or its supply from the overlying water through faunal burrows. However, the occurrence of the latter process was not confirmed by the profiles of other constituents. In the central Pacific Ocean, the accumulation of N₂O and NO₃⁻ in the sediments likely resulted from nitrification. Nitrous oxide fluxes from the sediments, calculated using its gradient at the sediment–water interface and the molecular diffusion coefficient, were −45 to 6.9 nmolN m⁻² h⁻¹ in Koaziro Bay in the spring, −29 to −21 nmolN m⁻² h⁻¹ in the summer, −46 to 37 nmolN m⁻² h⁻¹ in the East China Sea, 0.17 to 0.23 nmolN m⁻² h⁻¹ in the equatorial Pacific, and <±0.2 nmolN m⁻² h⁻¹ in the subtropical North Pacific, respectively.     

Nitrogen and oxygen isotopic composition of N2O from suboxic waters of the eastern tropical North Pacific and the Arabian Sea—measurement by continuous-flow isotope-ratio monitoring

Nitrous oxide (N₂O) is a trace gas that is increasing in the atmosphere. It contributes to the greenhouse effect and influences the global ozone distribution. Recent reports suggest that regions such as the Arabian Sea may be significant sources of atmospheric N₂O.In the ocean, N₂O is formed as a by-product of nitrification and as an intermediary of denitrification. In the latter process, N₂O can be further reduced to N₂. These processes, which operate on different source pools and have different magnitudes of isotopic fractionation, make separate contributions to the ¹⁵N and¹⁸O isotopic composition of N₂O. In the case of nitrification in oxic waters, the isotopic composition of N₂O appears to depend mainly on the ¹⁵N/¹⁴N ratio of NH⁺₄ and the ¹⁸O/¹⁶O ratio of O₂ and H₂O. In suboxic waters, denitrification causes progressive ¹⁵N and ¹⁸O enrichment of N₂O as a function of degree of depletion of nitrate and dissolved oxygen. Thus the isotopic signature of N₂O should be a useful tool for studying the sources and sinks for N₂O in the ocean and its impact on the atmosphere.We have made observations of N₂O concentrations and of the dual stable isotopic composition of N₂O in the eastern tropical North Pacific (ETNP) and the Arabian Sea. The stable isotopic composition of N₂O was determined by a new method that required only 80–100 nmol of N₂O per sample analysis. Our observations include determinations across the oxic/suboxic boundaries that occur in the water columns of the ETNP and Arabian Sea. In these suboxic waters, the values of δ¹⁵N and δ¹⁸O increased linearly with one another and with decreasing N₂O concentrations, presumably reflecting the effects of denitrification. Our results suggest that the ocean could be an important source of isotopically enriched N₂O to the atmosphere.     

Benthic fluxes of nitrogen in the tidal reaches of a turbid, high-nitrate sub-tropical river

Benthic fluxes of dissolved inorganic nitrogen (NO₃⁻ and NH₄⁺), dissolved organic nitrogen (DON), N₂ (denitrification), O₂ and TCO₂ were measured in the tidal reaches of the Bremer River, south east Queensland, Australia. Measurements were made at three sites during summer and winter. Fluxes of NO₃⁻ were generally directed into the sediments at rates of up to −225 μmol N m⁻² h⁻¹. NH₄⁺ was mostly taken up by the sediments at rates of up to −52 μmol N m⁻² h⁻¹, its ultimate fate probably being denitrification. DON fluxes were not significant during winter. During summer, fluxes of DON were observed both into (−105 μmol m⁻² h⁻¹) and out of (39 μmol m⁻² h⁻¹) the sediments. Average N₂ fluxes at all sampling sites were similar during summer (162 μmol N m⁻² h⁻¹) and winter (153 μmol N m⁻² h⁻¹). Denitrification was fed both by nitrification within the sediment and NO₃⁻ from the water column. Sediment respiration rates played an important role in the dynamics of nitrification and denitrification. NO₃⁻ fluxes were significantly related to TCO₂ fluxes (p<0.01), with a release of NO₃⁻ from the sediment only occurring at respiration rates below 1000 μmol C m⁻² h⁻¹. Rates of denitrification increased with respiration up to TCO₂ fluxes of 1000 μmol C m⁻² h⁻¹. At sediment respiration rates above 1000 μmol C m⁻² h⁻¹, denitrification rates increased less rapidly with respiration in winter and declined during summer. On a monthly basis denitrification removed about 9% of the total nitrogen and 16% of NO₃⁻ entering the Bremer River system from known point sources. This is a similar magnitude to that estimated in other tidal river systems and estuaries receiving similar nitrogen loads. During flood events the amount of NO₃⁻ denitrified dropped to about 6% of the total river NO₃⁻ load.     

Microbial photosynthesis in coral reef sediments (Heron Reef, Australia)

We investigated microphytobenthic photosynthesis at four stations in the coral reef sediments at Heron Reef, Australia. The microphytobenthos was dominated by diatoms, dinoflagellates and cyanobacteria, as indicated by biomarker pigment analysis. Conspicuous algae firmly attached to the sand grains (ca. 100 μm in diameter, surrounded by a hard transparent wall) were rich in peridinin, a marker pigment for dinoflagellates, but also showed a high diversity based on cyanobacterial 16S rDNA gene sequence analysis. Specimens of these algae that were buried below the photic zone exhibited an unexpected stimulation of respiration by light, resulting in an increase of local oxygen concentrations upon darkening. Net photosynthesis of the sediments varied between 1.9 and 8.5 mmol O₂ m⁻² h⁻¹ and was strongly correlated with Chl a content, which lay between 31 and 84 mg m⁻². An estimate based on our spatially limited dataset indicates that the microphytobenthic production for the entire reef is in the order of magnitude of the production estimated for corals. Photosynthesis stimulated calcification at all investigated sites (0.2–1.0 mmol Ca²⁺ m⁻² h⁻¹). The sediments of at least three stations were net calcifying. Sedimentary N₂-fixation rates (measured by acetylene reduction assays at two sites) ranged between 0.9 to 3.9 mmol N₂ m⁻² h⁻¹ and were highest in the light, indicating the importance of heterocystous cyanobacteria. In coral fingers no N₂-fixation was measurable, which stresses the importance of the sediment compartment for reef nitrogen cycling.     

Nitrogen cycling in deep-sea sediments of the Porcupine Abyssal Plain, NE Atlantic

Rates of transformation, recycling and burial of nitrogen and their temporal and spatial variability were investigated in deep-sea sediments of the Porcupine Abyssal Plain (PAP), NE Atlantic during eight cruises from 1996 to 2000. Benthic fluxes of ammonium (NH₄) and nitrate (NO₃) were measured in situ using a benthic lander. Fluxes of dissolved organic nitrogen (DON) and denitrification rates were calculated from pore water profiles of DON and NO₃, respectively. Burial of nitrogen was calculated from down core profiles of nitrogen in the solid phase together with ¹⁴C-based sediment accumulation rates and dry bulk density. Average NH₄ and NO₃-effluxes were 7.4 ± 19 μmol m⁻² d⁻¹ (n = 7) and 52 ± 30 μmol m⁻² d⁻¹ (n = 14), respectively, during the period 1996–2000. During the same period, the DON-flux was 11 ± 5.6 μmol m⁻² d⁻¹ (n = 5) and the denitrification rate was 5.1 ± 3.0 μmol m⁻² d⁻¹ (n = 22). Temporal and spatial variations were only found in the benthic NO₃ fluxes. The average burial rate was 4.6 ± 0.9 μmol m⁻² d⁻¹. On average over the sampling period, the recycling efficiency of the PON input to the sediment was 94% and the burial efficiency hence 6%. The DON flux constituted 14% of the nitrogen recycled, and it was of similar magnitude as the sum of burial and denitrification. By assuming the PAP is representative of all deep-sea areas, rates of denitrification, burial and DON efflux were extrapolated to the total area of the deep-sea floor (>2000 m) and integrated values of denitrification and burial of 8 ± 5 and 7 ± 1 Tg N year⁻¹, respectively, were obtained. This value of total deep-sea sediment denitrification corresponds to 3–12% of the global ocean benthic denitrification. Burial in deep-sea sediments makes up at least 25% of the global ocean nitrogen burial. The integrated DON flux from the deep-sea floor is comparable in magnitude to a reported global riverine input of DON suggesting that deep-sea sediments constitute an important source of DON to the world ocean.     

Anomalously low alkenone temperatures caused by lateral particle and sediment transport in the Malvinas Current region, western Argentine Basin

We analysed the alkenone unsaturation ratio (U^K′₃₇) in 87 surface sediment samples from the western South Atlantic (5°N–50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured U^K′₃₇ ratios were converted into temperature using the global core-top calibration of Müller et al. (1998) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by −2° to −6°C are found in the regions of the Brazil–Malvinas Confluence (35–39°S) and the Malvinas Current (41–48°S). From the oceanographic evidence these low U^K′₃₇ values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating U^K′₃₇ temperatures. In this way, particles and sediments carrying a cold water U^K′₃₇ signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.     

N2, N2O and O2Profiles in a Tagus Estuary Salt Marsh

Vertical gas profiles of N₂, N₂O and O₂were obtained in intact sediment cores from a Tagus estuary salt marsh using membrane inlet mass spectrometry. This technique allows direct measurements of dissolved gas concentrations with minimal disturbance. O₂concentrations decreased sharply with depth, becoming undetectable below 14mm. Denitrification products (N₂and N₂O) occurred in the surface layer of the sediment where O₂was present. Diffusion of N₂and N₂O from the anaerobic zone, denitrification in anaerobic microsites and aerobic denitrification are possible explanations for this observation. N₂was the sole product of denitrification in control sediment cores probably because of the great demand for electron acceptors in this sediment. The addition of NO₃ ⁻ and CH₃CO₂ ⁻ increased the concentrations of N₂and N₂O in the sediment. Significantly higher concentrations in treated cores occurred between 1·5 and 2·0cm for N₂and between 0·5 and 1·5cm for N₂O. The peak in N₂concentration occurred in the anaerobic zone of the sediment, close to the aerobic–anaerobic interface while the peak in N₂O concentration occurred above this interface where concentrations of O₂were approximately 10μM. This is indicative that, in this sediment, production of N₂O is less sensitive to the presence of O₂than reduction of N₂O to N₂.     

Effects of irradiance on benthic and water column processes in a Gulf of Mexico estuary: Pensacola Bay, Florida, USA

We examined the effect of light on water column and benthic fluxes in the Pensacola Bay estuary, a river-dominated system in the northeastern Gulf of Mexico. Measurements were made during the summers of 2003 and 2004 on 16 dates distributed along depth and salinity gradients. Dissolved oxygen fluxes were measured on replicate sediment and water column samples exposed to a gradient of photosynthetically active radiation. Sediment inorganic nutrient (NH₄⁺, NO₃⁻, PO₄³⁻) fluxes were measured. The response of dissolved oxygen fluxes to variation in light was fit to a photosynthesis–irradiance model and the parameter estimates were used to calculate daily integrated production in the water column and the benthos. The results suggest that shoal environments supported substantial benthic productivity, averaging 13.6 ± 4.7 mmol O₂ m⁻² d⁻¹, whereas channel environments supported low benthic productivity, averaging 0.5 ± 0.3 mmol O₂ m⁻² d⁻¹ (±SE). Estimates of baywide microphytobenthic productivity ranged from 8.1 to 16.5 mmol O₂ m⁻² d⁻¹, comprising about 16–32% of total system productivity. Benthic and water column dark respiration averaged 15.2 ± 3.2 and 33.6 ± 3.7 mmol O₂ m⁻² d⁻¹, respectively Inorganic nutrient fluxes were generally low compared to relevant estuarine literature values, and responded minimally to light exposure. Across all stations, nutrient fluxes from sediments to the water column averaged 1.11 ± 0.98 mmol m⁻² d⁻¹ for NH₄⁺, 0.58 ± 1.08 mmol m⁻² d⁻¹ for NO₃⁻, 0.01 ± 0.09 mmol m⁻² d⁻¹ for PO₄³⁻. The results of this study illustrate how light reaching the sediments is an important modulator of benthic nutrient and oxygen dynamics in shallow estuarine systems.     

The effects of semi-lunar spring and neap tidal change on nitrification, denitrification and N2O vertical distribution in the intertidal sediments of the Yangtze estuary, China

To explore the influences of semi-lunar spring and neap tidal changes on nitrogen cycling in intertidal sediments, a comparative study among waterlogged, desiccated and reflooded systems was carried out in August 2005 and February 2006 by analyzing nitrification, denitrification and N₂O depth profiles in the intertidal flats of the Yangtze estuary. Laboratory experiments showed that alternating emersion and inundation resulted in the significant changes in nitrification and denitrification rates in the intertidal sediment systems. Due to the desiccation-related effects, lowest nitrification and denitrification rates were observed in the desiccated sediment cores. Highest nitrification and denitrification rates were however detected in the waterlogged and reflooded systems, respectively. It is hypothesized that the highest nitrification rates in the waterlogged sediments were mainly attributed to higher nitrifier numbers and NH₄⁺ being more available, whereas the availability of NO₃⁻ might dominate denitrification in the reflooded sediments. In addition, the highest N₂O concentrations were detected in the reflooded sediment cores, and the lowest found in the dried sediment cores. It was also shown that N₂O in the intertidal sediments was mainly from nitrification under the desiccated condition. In contrast, N₂O in the intertidal sediments was produced mainly via denitrification under the waterlogged and reflooded conditions. It is therefore concluded that the semi-lunar tidal cycle has a significant influence on nitrification, denitrification and N₂O production in the intertidal sediment systems.     

Benthic primary production, respiration and remineralisation: in situ measurements in the soft-bottom Abra alba community of the western English Channel (North Brittany)

In situ measurements of ammonium and carbon dioxide fluxes were performed using benthic chambers at the end of spring and the end of summer in two soft-bottom Abra alba communities of the western English Channel (North Brittany): the muddy sand community (5 m, about 10% of surface irradiance) and the fine-sand community (19 m, about 1% of surface irradiance). High rates of ammonium regeneration were measured in the two communities at the end of summer (296.03±40.07 and 201.7±62.74 μmolN m⁻² h⁻¹, respectively) as well as high respiration rates (2.60±0.94 and 2.23±0.59 mmolC m⁻² h⁻¹, respectively). Significant benthic gross primary production (up to 6.11 mmolC m⁻² h⁻¹) was measured in the muddy sand community but no benthic primary production was measured in the fine-sand community. It suggests that microphytobenthic production values used in simulations previously published for these two communities were overestimated while values of community respiration were underestimated. The study confirms that this benthic system is heterotrophic and strengthens the idea that an important pelagic-benthic coupling is required for the functioning in such coastal ecosystems.     

Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).     

Distinctive C isotopic signature distinguishes a novel sea ice biomarker in Arctic sediments and sediment traps

A C₂₅ highly branched isoprenoid (HBI) monoene hydrocarbon, designated IP₂₅, has been proposed previously to originate from diatoms living in Arctic sea ice, while the presence of IP₂₅ in sediments has been suggested to be a proxy for the occurrence of former Arctic sea ice. Here, we show that the ¹³C isotopic composition of IP₂₅ in sea ice, in sediment trap material collected under sea ice, and in high latitude northern sediments, is distinctive (isotopically ‘heavy’) and distinguishable from that of organic matter of planktonic or terrigenous origin. Mean δ¹³C values for IP₂₅ were − 22.3 ± 0.4‰ (sea ice), − 19.6 ± 1.1‰ (sediment traps) and − 19.3 ± 2.3‰ (sediments). These measurements, therefore, support further the proposed use of IP₂₅ as an Arctic sea ice proxy.     

Eutrophication and the rate of net nitrification in a coastal marine ecosystem

Rates of net nitrification were calculated for four large (13 m³) estuarine-based microcosms that had been subjected to inorganic nutrient enrichment. Calculated rates were based on two years of weekly nitrate and nitrite measurements and ranged from a maximum of 0·55 μmol NO₂₊₃⁻ produced l⁻¹ day⁻¹ in the control tank (no enrichment) to over 13 μmol NO₂₊₃⁻ produced l⁻¹ day⁻¹ in the most enriched tank (receiving 18·6 μmol NH₄ l⁻¹ day⁻¹). Almost all NO₂₊₃⁻ production was pelagic, little was benthic. Net NO₃⁻ production or net NO₂⁻ production dominated the net nitrification rates during different seasons. Good correlations were found between various oxidation rates and substrate concentrations. The calculated net nitrite production rates were 10 to 1000 times higher than previously reported rates for open ocean systems, demonstrating the potential importance of nitrification to estuarine systems.     

Seasonal variations of alkenones and U37 in the Chesapeake Bay water column

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.     

Uptake of atmospheric carbon dioxide in Arctic shelf seas: evaluation of the relative importance of processes that influence pCO2 in water transported over the Bering–Chukchi Sea shelf

The uptake of atmospheric carbon dioxide in the water transported over the Bering–Chukchi shelves has been assessed from the change in carbon-related chemical constituents. The calculated uptake of atmospheric CO₂ from the time that the water enters the Bering Sea shelf until it reaches the northern Chukchi Sea shelf slope (1 year) was estimated to be 86±22 g C m⁻² in the upper 100 m. Combining the average uptake per m³ with a volume flow of 0.83×10⁶ m³ s⁻¹ through the Bering Strait yields a flux of 22×10¹² g C year⁻¹. We have also estimated the relative contribution from cooling, biology, freshening, CaCO₃ dissolution, and denitrification for the modification of the seawater pCO₂ over the shelf. The latter three had negligible impact on pCO₂ compared to biology and cooling. Biology was found to be almost twice as important as cooling for lowering the pCO₂ in the water on the Bering–Chukchi shelves. Those results were compared with earlier surveys made in the Barents Sea, where the uptake of atmospheric CO₂ was about half that estimated in the Bering–Chukchi Seas. Cooling and biology were of nearly equal significance in the Barents Sea in driving the flux of CO₂ into the ocean. The differences between the two regions are discussed. The loss of inorganic carbon due to primary production was estimated from the change in phosphate concentration in the water column. A larger loss of nitrate relative to phosphate compared to the classical ΔN/ΔP ratio of 16 was found. This excess loss was about 30% of the initial nitrate concentration and could possibly be explained by denitrification in the sediment of the Bering and Chukchi Seas.     

Flux of Reduced Sulfur Gases Along a Salinity Gradient in Louisiana Coastal Marshes

Seasonal and diurnal reduced sulfur gas emissions were measured along a salinity gradient in Louisiana Gulf Coast salt, brackish and freshwater marshes. Reduced sulfur gas emission was strongly associated with habitat and salinity gradient. The dominant emission component was dimethyl sulfide (average: 57·3 μg S m⁻² h⁻¹) in saltmarsh with considerable seasonal (max: 144·03 μg S m⁻² h⁻¹; min: 1·47 μg S m⁻² h⁻¹) and diurnal (max: 83·58 μg S m⁻² h⁻¹; min: 69·59 μg S m⁻² h⁻¹) changes in flux rates. Hydrogen sulfide was dominant (average: 21·2 μg S m⁻² h⁻¹, max: 79·2 μg S m⁻² h⁻¹; min: 5·29 μg S m⁻² h⁻¹) form in brackishmarsh and carbonyl sulfide (average: 1·09 μg S m⁻² h⁻¹; max: 3·42 μg S m⁻² h⁻¹; min: 0·32 μg S m⁻² h⁻¹) was dominant form in freshwater marsh. A greater amount of H₂S was evolved from brackishmarsh (21·22 μg S m⁻² h⁻¹) as compared to the saltmarsh (2·46 μg S m⁻² h⁻¹) and freshwater marsh (0·30 μg S m⁻² h⁻¹). Emission of total reduced sulfur gases decreased with decrease in salinity and distance inland from the coast. Emission of total reduced sulfur gases over the study averaged 73·3 μg S m⁻² h⁻¹ for the saltmarsh, 32·1 μg S m⁻² h⁻¹ for brackishmarsh and 2·76 μg S m⁻² h⁻¹ for the freshwater marsh.     

fCO2 variability at the CARIACO tropical coastal upwelling time series station

Monthly seawater pH and alkalinity measurements were collected between January 1996 and December 2000 at 10°30′N, 64°40′W as part of the CARIACO (CArbon Retention In A Colored Ocean) oceanographic time series. One key objective of CARIACO is to study temporal variability in Total CO₂ (TCO₂) concentrations and CO₂ fugacity (fCO₂) at this tropical coastal wind-driven upwelling site. Between 1996 and 2000, the difference between atmospheric and surface ocean CO₂ concentrations ranged from about − 64.3 to + 62.3 μatm. Physical and biochemical factors, specifically upwelling, temperature, primary production, and TCO₂ concentrations interacted to control temporal variations in fCO₂. Air–sea CO₂ fluxes were typically depressed (0 to + 10 mmol C m^{− 2} day^{− 1}) in the first few months of the year during upwelling. Fluxes were higher during June–November (+ 10 to 20 mmol C m^{− 2} day^{− 1}). Fluxes were generally independent of the slight changes in salinity normally seen at the station, but low positive flux values were seen in the second half of 1999 during a period of anomalously heavy rains and land-derived runoff. During the 5 years of monthly data examined, only two episodes of negative air–sea CO₂ flux were observed. These occurred during short but intense upwelling events in March 1997 (−10 mmol C m^{− 2} day^{− 1}) and March 1998 (− 50 mmol C m^{− 2} day^{− 1}). Therefore, the Cariaco Basin generally acted as a source of CO₂ to the atmosphere in spite of primary productivity in excess of between 300 and 600 g C m^{− 2} year^{− 1}.     

Annual Primary Production in Narragansett Bay with no Bay-Wide Winter–Spring Phytoplankton Bloom

Primary production was estimated over the annual cycle from ¹⁴C incubations conducted in 5 m deep enclosures and modeled for 16 stations in Narragansett Bay with data from biweekly surveys in which light, chlorophyll, attenuation coefficients and other parameters were measured. Annual values ranged from 160 g C m⁻² y⁻¹ in the lower West Passage to 619 g C m⁻² y⁻¹ at the mouth of the Providence River. The annual bay-wide, area mean fell near the middle of this range at 323 g C m⁻² y⁻¹ and was not apparently different from previous surveys. In the 1998 warm, El Niño winter, no bay-wide winter–spring phytoplankton flowered. Bloom limitation was correlated with warm temperatures which may have stimulated grazing rates. The lack of a bloom did not change annual levels of primary production but this alteration in carbon flow may impact macrofauna in the benthic infauna community.     

Organic carbon and iron modulate nitrification rates in mangrove swamps of Goa, south west coast of India

Nitrification, fuelled by ammonium is the pivotal oxidative pathway to nitrogen cycling. In spite of its ecological significance, the factors regulating nitrification rates in the benthic realm remain poorly understood. The present study therefore examines some of the factors like ammonium, nitrite, nitrate, organic carbon, iron and manganese on down-core variability in benthic nitrification rates in two different mangrove ecosystems, one under the influence of ferromanganese ore mining (experiment) and the other relatively undisturbed (control). We hypothesize that besides organic carbon, iron could also influence the rate of nitrification. The study also contrasts the distributive pattern of autotrophic and heterotrophic nitrifiers in the two regions. The concentration of iron at the control site ranged from 1.1% to 15.1% while at the experimental site it ranged from 2.9% to 46%. The levels of organic carbon at control and experimental sites ranged from 0.02% to 6.9% and 0.1% to 6.5%, respectively. The nitrification rates at the control and experimental sites are comparable and ranged from 3.2 ± 1.2 to 18.4 ± 1.9 ng at-N g(sediment)⁻¹ h⁻¹ and 2.7 ± 1.5 to 18.2 ± 0.6 ng at-N g(sediment)⁻¹ h⁻¹, respectively. While the abundance of heterotrophic nitrifiers at both the sites ranged from 10^2–3 cells g⁻¹ sediment, the autotrophic nitrifiers at the experimental site was higher by an order at 10³ cells g⁻¹ sediment reflecting the relatively higher refractile nature of organic carbon at the experimental site (Straus and Lamberti, 2000). Though organic carbon and nitrification rates are similar in both the sites, the underlying mechanisms governing the processes could be different. Our studies suggest that at the control site, heterotrophic nitrifiers govern nitrification rates (r = 0.28, p < 0.05, n = 64) using organic carbon (r = 0.32, p < 0.01, n = 64). At the experimental site, nitrification was governed more by autotrophic nitrifiers (r = 0.43, p < 0.001, n = 64) at the expense of iron (r = 0.47, p < 0.001, n = 64). Therefore at the experimental site with higher load of iron, autotrophic nitrification could be more important. It is therefore inferred that both the quality of organic carbon and quantity of iron govern nitrification rates in these mangrove swamps.     

High-resolution measurement of Southern Ocean CO2 and O2/Ar by membrane inlet mass spectrometry

This paper evaluates the simultaneous measurement of dissolved gases (CO₂ and O₂/Ar ratios) by membrane inlet mass spectrometry (MIMS) along the 180° meridian in the Southern Ocean. The calibration of pCO₂ measurements by MIMS is reported for the first time using two independent methods of temperature correction. Multiple calibrations and method comparison exercises conducted in the Southern Ocean between New Zealand and the Ross Sea showed that the MIMS method provides pCO₂ measurements that are consistent with those obtained by standard techniques (i.e. headspace equilibrator equipped with a Li–Cor NDIR analyser). The overall MIMS accuracy compared to Li–Cor measurements was 0.8 μatm. The O₂/Ar ratio measurements were calibrated with air-equilibrated seawater standards stored at constant temperature (0 ± 1 °C). The reproducibility of the O₂/Ar standards was better than 0.07% during the 9 days of transect between New Zealand and the Ross Sea.The high frequency, real-time measurements of dissolved gases with MIMS revealed significant small-scale heterogeneity in the distribution of pCO₂ and biologically-induced O₂ supersaturation (ΔO₂/Ar). North of 65°S several prominent thermal fronts influenced CO₂ concentrations, with biological factors also contributing to local variability. In contrast, the spatial variation of pCO₂ in the Ross Sea gyre was almost entirely attributed to the biological utilization of CO_2, with only small temperature effects. This high productivity region showed a strong inverse relationship between pCO₂ and biologically-induced O₂ disequilibria (r² = 0.93). The daily sea air CO₂ flux ranged from − 0.2 mmol/m² in the Northern Sub-Antarctic Front to − 6.4 mmol/m² on the Ross Sea shelves where the maximum CO₂ influx reached values up to − 13.9 mmol/m². This suggests that the Southern Ocean water (south of 58°S) acts as a seasonal sink for atmospheric CO₂ at the time of our field study.